Lubricants from Mixed Alpha-Olefin Feeds

ABSTRACT

This invention discloses an improved process which employs mixed alpha-olefins as feed over activated metallocene catalyst systems to provide essentially random liquid polymers particularly useful in lubricant components or as functional fluids

FIELD OF THE INVENTION

The invention relates to lubricant compositions comprising PAO and/orHVI-PAO basestock made by contacting mixed feed alpha-olefins with acatalyst comprising a metallocene.

BACKGROUND OF THE INVENTION

The viscosity-temperature relationship of a lubricating oil is one ofthe critical criteria which must be considered when selecting alubricant for a particular application. Viscosity Index (VI) is anempirical, unitless number which indicates the rate of change in theviscosity of an oil within a given temperature range. Fluids exhibitinga relatively large change in viscosity with temperature are said to havea low viscosity index. A low VI oil, for example, will thin out atelevated temperatures faster than a high VI oil. Usually, the high VIoil is more desirable because it has higher viscosity at highertemperature, which translates into better or thicker lubrication filmand better protection of the contacting machine elements. In anotheraspect, as the oil operating temperature decreases, the viscosity of ahigh VI oil will not increase as much as the viscosity of a low VI oil.This is advantageous because the excessive high viscosity of the low VIoil will decrease the efficiency of the operating machine. Thus high VIoil has performance advantages in both high and low temperatureoperation. VI is determined according to ASTM method D 2270-93 [1998].VI is related to kinematic viscosities measured at 40° C. and 100° C.using ASTM Method D 445.

PAOs comprise a class of hydrocarbons manufactured by the catalyticoligomerization (polymerization to low molecular weight products) oflinear α-olefins (LAOs) typically ranging from 1-hexene to 1-octadecene,more typically from 1-octene to 1-dodecene, with 1-decene as the mostcommon and often preferred material. Such fluids are described, forexample, in U.S. Pat. No. 6,824,671 and patents referenced therein,although polymers of lower olefins such as ethylene and propylene mayalso be used, especially copolymers of ethylene with higher olefins, asdescribed in U.S. Pat. No. 4,956,122 or 4,990,709 and the patentsreferred to therein.

High viscosity index polyalpha-olefin (HVI-PAO) prepared by, forinstance, polymerization of alpha-olefins using reduced metal oxidecatalysts (e.g., chromium) are described, for instance, in U.S. Pat.Nos. 4,827,064; 4,827,073; 4,990,771; 5,012,020; and 5,264,642. TheseHVI-PAOs are characterized by having a high viscosity index (VI) ofabout 130 and above, more preferably 150 and above, still morepreferably 160 and above, yet still more preferably 200 and above, andone or more of the following characteristics: a branch ratio of lessthan 0.19, a weight average molecular weight of between 300 and 45,000,a number average molecular weight of between 300 and 18,000, a molecularweight distribution of between 1 and 5, and pour point below −15° C.Measured in carbon number, these molecules range from C₃₀ to C₁₃₀₀.Viscosities of the HVI-PAO oligomers measured at 100° C. range from 3centistokes (“cSt”) to 15,000 cSt. These HVI-PAOs have been used asbasestocks in engine and industrial lubricant formulations. See alsoU.S. Pat. Nos. 4,180,575; 4,827,064; 4,827,073; 4,912,272; 4,990,771;5,012,020; 5,264,642; 6,087,307; 6,180,575; WO 03/09136; WO 2003071369A;U.S. Patent Application No. 2005/0059563; WO 00/58423; and LubricationEngineers, 55/8, 45 (1999); and have recently been found to be usefulfor industrial oil and grease formulations (e.g., U.S. patentapplication Ser. No. (yet to be assigned) [Attorney Docket No. 2005B085,filed Jun. 29, 2005].

Another advantageous property of these HVI-PAOs is that, while lowermolecular weight unsaturated oligomers are typically and preferablyhydrogenated to produce thermally and oxidatively stable materials,higher molecular weight unsaturated HVI-PAO oligomers useful aslubricant are sufficiently thermally and oxidatively stable to beutilized without hydrogenation and, optionally, may be so employed.

As used herein, the term “polyalpha-olefin” includes PAOs and HVI-PAOs.Depending on the context, the term “PAO” may include HVI-PAOs or it maybe used to distinguish non-HVI-PAOs from HVI-PAOs. Generally, when PAOis used alone, it implies the products have properties similar to thefluids made from conventional polymerization process using BF₃ or AlCl₃or their modified versions, as described in U.S. Pat. No. 6,824,671 andreferences therein.

Polyalpha-olefins of different viscosity grades are known to be usefulin synthetic and semi-synthetic lubricants and grease formulations. See,for instance, Chapters 19 to 27 in Rudnick et al., “Synthetic Lubricantsand High-Performance Functional Fluids”, 2nd Ed. Marcel Dekker, Inc.,N.Y. (1999). Compared to the conventional mineral oil-based products,these PAO-based products have excellent viscometrics, high and lowtemperature performance. They usually provide energy efficiency andextended service life.

In the production of PAOs and HVI-PAOs, the feed is usually limited toone specific alpha-olefins, usually 1-decene. Occasionally, when1-decene is not available in large enough quantity, small to moderateamounts of 1-octene or 1-dodecene is added to make up the quantity. Itis generally thought that 1-decene is the most preferred feed (seereference “Wide-Temperature Range Synthetic Hydrocarbon Fluids” by J. A.Brennen, Ind. Eng. Chem. Prod. Res. Dev., 19, 2-6 (1980). When mixturesof feed are used, the products tend to be blocky copolymers rather thanrandom copolymers and/or products produced at the beginning of theprocess are different than that produced at the end of the process, andthe inhomogeneous polymer product will be characterized by poorviscosity indices (VI) and poor low temperature properties are produced.Thus, in the past, PAOs and HVI-PAOs have generally been made using pureC₁₀ feeds.

There are specific examples of mixed feeds being used. For instance, inU.S. Pat. No. 6,646,174, a mixture of about 10 to 40 wt. % 1-decene andabout 60 to 90 wt. % 1-dodecene and are co-oligomerized in the presenceof an alcohol promoter. Preferably 1-decene is added portion-wise to thesingle oligomerization reactor containing 1-dodecene and a pressurizedatmosphere of boron trifluoride. Product is taken overhead and thevarious cuts are hydrogenated to give PAO characterized by a kinematicviscosity of from about 4 to about 6 at 100° C., a Noack weight loss offrom about 4% to about 9%, a viscosity index of from about 130 to about145, and a pour point in the range of from about −60° C. to about −50°C. See also U.S. Pat. Nos. 4,950,822; 6,646,174; 6,824,671, 5,382,739and U.S. Patent Application No. 2004/0033908. All these copolymers orco-oligomers produced by conventional Friedel-Crafts catalysts usuallyare characterized by having extra relatively short branches, such asmethyl and ethyl short side chains, even though the feed olefins do notcontain these short branches. This is because the Friedel-Craftscatalyst partially isomerizes the starting alpha-olefins and theintermediates formed during the oligomerization. The presence of shortchain branches is less desirable for superior lubricant properties,including VI and volatility. In contrast, the copolymers described inthis invention will not have extraneous short chain branches. If thefeed is propylene and 1-dodecene, the predominant side chain in thepolymers will be methyl and n-C₁₀H₂₃ side chains. Except for thecontribution of usually less than 5% of the polymer end groups initiatedthrough the rare allylic hydrogen abstraction of the alpha-olefinmonomers by the active metal centers, the oligomers will not have extraethyl, propyl, butyl, etc. side chains that are present innon-metallocene (e.g. Friedel-Crafts) methods.

Previous patents report the use of mixed alpha-olefins as feeds toproduced co-oligomers or copolymers for use as lubricant components.U.S. Pat. No. 4,827,073 reported the use of a reduced chromium oxide onsilica gel as catalyst to polymerize C₆ to C₂₀ alpha-olefins. Althoughliquid copolymers were produced by the process, the copolymer has verydifferent polymer composition from the monomer ratio in the feed. Thereduced chromium oxide on silica gel catalyst polymerized the loweralpha-olefins, such as 1-butene or 1-hexene, at a significantly higherrate than the alpha-olefins of 1-decene, 1-dodecene or largeralpha-olefins [see comparative examples in Example section]. As aresult, the copolymer tends to be more blocky or more inhomogeneous in aconventional synthesis process. Both are detrimental to the product VIand low temperature properties. Similarly, Ziegler or Ziegler-Natta typecatalysts have also been reported to copolymerize mixed alpha-olefins.Examples are U.S. Pat. Nos. 4,132,663, 5,188,724 and 4,163,712. Theproblem with using Ziegler or Ziegler-Natta catalysts is that they canonly produce polymers of very high molecular weights. As a result, theproducts are used as plastics and additives, but are not suitable ashigh performance base stocks. Furthermore, according to all literaturereports, Ziegler or Ziegler-Natta catalysts usually have higherreactivities toward smaller alpha-olefins, such as propylene, 1-butene,1-pentene or 1-hexene, than toward larger alpha-olefins, such as1-decene, 1-dodecene, or larger 1-olefins (reference MacromolecularChemistry and Physics, 195, 2805 (1994) or 195, 3889 (1994)). Thisdifference in catalyst reactivity resulted in heterogeneous chemicalstructures for the copolymers, which are not random copolymers and havehigh degree of blockiness. Both characteristics are detrimental for lubeproperties.

It would be highly beneficial if a process could be devised whereby ahomogeneous and uniform PAO and/or HVI-PAO having an excellentviscosity-temperature relationship could be produced from a wide varietyof mixed feed LAOs.

The present inventors have discovered an unanticipated method ofproducing a uniform PAO and/or HVI-PAO product by contacting a mixedfeed of LAOs of varying carbon numbers with an activated metallocenecatalyst.

SUMMARY OF THE INVENTION

The invention is directed to an improved process for producing PAOs andHVI-PAOs which employs contacting a feed comprising a mixture of LAOswith an activated metallocene catalyst, optionally after hydrogenation,to produce liquid polymers with superior properties for use as lubricantcomponents or as functional fluids.

This invention is also directed to a copolymer composition made from atleast two alpha-olefins of C₃ to C₃₀ range and having monomers randomlydistributed in the polymers. It is preferred that the average carbonnumber, as defined herein, is at least 4.1. Advantageously, ethylene andpropylene, if present in the feed, are present in the amount of lessthan 50 wt % individually or preferably less than 50 wt % combined. Thecopolymers of the invention can be isotactic, atactic, syndiotacticpolymers or any other form of appropriate tacticity. These copolymershave useful lubricant properties, including excellent VI, pour point,low temperature viscometrics when used alone, or as blend fluids withother lubricants or other polymers. Furthermore, these copolymers havenarrow molecular weight distributions and excellent shear stability.

In an embodiment, the mixed feed LAOs comprise at least two and up to 26different linear alpha-olefins selected from C₃ to C₃₀ linearalpha-olefins. In a preferred embodiment, the mixed feed LAO is obtainedfrom an ethylene growth process using an aluminum catalyst or ametallocene catalyst.

In another embodiment, the alpha-olefins can be chosen from anycomponent from a conventional LAO production facility together withanother LAO available from a refinery or chemical plant, includingpropylene, 1-butene, 1-pentene, and the like, or with 1-hexene or1-octene made from dedicated production facility. In another embodiment,the alpha-olefins can be chosen from the alpha-olefins produced fromFischer-Tropsch synthesis (as reported in U.S. Pat. No. 5,382,739).

The activated metallocene catalyst can be simple metallocenes,substituted metallocenes or bridged metallocene catalysts activated orpromoted by, for instance, MAO or a non-coordinating anion.

It is an object of the invention to provide a convenient method ofmaking a new PAO and/or HVI-PAO composition from a variety offeedstocks.

These and other objects, features, and advantages will become apparentas reference is made to the following detailed description, preferredembodiments, examples, and appended claims.

BRIEF DESCRIPTION OF THE DRAWINGS

In the accompanying drawings, like reference numerals are used to denotelike parts throughout the several views.

FIG. 1 illustrates the relationship of pour point versus kinematicviscosity for embodiments according to the present invention incomparison with a product produced using a pure C₁₀ feed.

FIG. 2 illustrates the relationship of viscosity index (VI) versuskinematic viscosity for embodiments according to the present inventioncompared with a product produced using a pure C₁₀ feed.

FIGS. 3 and 4 show the mole fraction of an olefin component in theproduct versus the mole fraction of same monomer in the feed forexamples according to the present invention.

FIG. 5 is a comparison of pour points between the prior art andembodiments of the invention

DETAILED DESCRIPTION

According to the invention, a feed comprising a mixture of LAOs selectedfrom C₃ to C₃₀ LAOs is contacted with an activated metallocene catalystunder oligomerization conditions to provide a liquid product, suitablefor use in lubricant components or as functional fluids, optionallyafter hydrogenation. This invention is also directed to a copolymercomposition made from at least two alpha-olefins of C₃ to C₃₀ range andhaving monomers randomly distributed in the polymers. The phrase “atleast two alpha-olefins” will be understood to mean “at least twodifferent alpha-olefins” (and similarly “at least three alpha-olefins”means “at least three different alpha-olefins”, and so forth).

In preferred embodiments, the average carbon number (defined hereinbelow) of said at least two alpha-olefins in said feed is at least 4.1.In another preferred embodiment, the amount of ethylene and propylene insaid feed is less than 50 wt % individually or preferably less than 50wt % combined. A still more preferred embodiment comprises a feed havingboth of the aforementioned preferred embodiments, i.e., a feed having anaverage carbon number of at least 4.1 and wherein the amount of ethyleneand propylene is less than 50 wt % individually.

In embodiments, the product obtained is an essentially random liquidcopolymer comprising the at least two alpha-olefins. By “essentiallyrandom” is meant that one of ordinary skill in the art would considerthe products to be a random copolymer. Other characterizations ofrandomness, some of which are preferred or more preferred, are providedherein. Likewise the term “liquid” will be understood by one of ordinaryskill in the art, but more preferred characterizations of the term areprovided herein. In describing the products as “comprising” a certainnumber of alpha-olefins (at least two different alpha-olefins), one ofordinary skill in the art in possession of the present disclosure wouldunderstand that what is being described in the polymerization (oroligomerization) product incorporating said certain number ofalpha-olefin monomers. In other words, it is the product obtained bypolymerizing or oligomerizing said certain number of alpha-olefinmonomers.

The descriptions herein follow the Periodic Table of the Elements as setout in Chemical and Engineering News, 63(5), 27 (1985).

LAO Feed

By “mixture of LAOs” is meant that at least two different linearalpha-olefins are present in the feed and up to 28 different linearalpha-olefins are present in the feed. It is a surprising discovery ofthe present invention that the rate of incorporation of monomers intothe polymer backbone is substantially the same regardless of the carbonnumber of the linear alpha-olefin, and it is further a surprisingdiscovery that the incorporation of monomers in the polymer chain isessentially random. This allows for a tremendous advantage in selectingthe feed composition to achieve a preselected target product. This alsoallows the advantage of producing a new copolymer composition with asubstantially random monomer distribution, resulting in superiorviscometric properties at both high and low temperature range.

In embodiments where the feed is selected from C₃ to C₃₀ LAOs, the feedwill comprise anywhere from 2 to 28 different LAOs. Thus, the feed maycomprise at least two, or at least three, or at least four, or at leastfive, or at least six, or at least seven, or at least eight, and so on,different feeds. The embodiments may be further characterized by havingno single LAO present in an amount greater than 80 wt %, 60 wt %, 50 wt%, or 49 wt %, or 40 wt %, or 33 wt %, or 30 wt %, or 25 wt %, or 20 wt%.

The amounts of LAO present in a feed will be specified herein as percentby weight of the entire amount of LAO in the feed, unless otherwisespecified. Thus, it will be recognized that the feed may also comprisean inert (with respect to the oligomerization reaction in question)material, such as a carrier, a solvent, or other olefin componentspresent that is not an LAO. Examples are propane, n-butane, iso-butane,cis- or trans-2-butenes, iso-butenes, and the like, that maybe presentwith propylene or with 1-butene feed. Other examples are the impurityinternal olefins or vinylidene olefins that are present in the LAO feed.

It is preferred that the amount of ethylene in said feed be at leastless than 50 wt % and generally much less than that, e.g., less than 5wt %, more preferably less than 4 wt % or less than 3 wt % or less than2 wt %, or less than 1 wt %. In preferred embodiment, the amount of bothethylene and propylene, on an individual basis, should be less than 50wt % and more preferably the combination of ethylene and propyleneshould be less than 50 wt %, more preferably less than 40 wt %, or 30 wt%, or 20 wt %, or 10 wt %, or 5 wt %.

In other embodiments, feeds may be advantageously selected from C₃ toC₃₀ LAOs, C₄ to C₂₄ LAOs, C₅ to C₂₄, C₄ to C₁₆ LAOs, C₅ to C₁₈, C₅ toC₁₆, C₆ to C₂₀ LAOs, C₄ to C₁₄ LAOs, C₅ to C₁₆, C₅ to C₁₆, C₆ to C₁₆LAOs, C₆ to C₁₈ LAOs, C₆ to C₁₄ LAOs, among other possible LAO feedsources, such as any lower limit listed herein to any upper limit listedherein. In other embodiments, the feed will comprise at least onemonomer selected from propylene, 1-butene, 1-pentene, 1-hexene to1-heptene and at least one monomer selected from C₁₂-C₁₈ alpha-olefins.Optionally one monomer is selected from C₈ and C₁₀ alpha-olefins. Apreferred embodiment is a feed comprising 1-hexene and 1-dodecene,1-tetradecene, and mixtures thereof. Another preferred embodiment is afeed comprising 1-butene and 1-dodecene, 1-tetradecene, and mixturesthereof. Another preferred embodiment is a feed comprising 1-hexene,1-decene, 1-dodecene and 1-tetradecene, and mixtures thereof. Anotherpreferred embodiment is a feed comprising 1-hexene and 1-octene,1-dodecene and 1-tetradecene, and mixtures thereof. Another preferredembodiment is a feed comprising 1-butene and 1-hexene and 1-dodecene,1-tetradecene, and mixtures thereof.

A particularly advantaged feedstock from the standpoint of supply andavailability is 1-hexene. There are many source of 1-hexene. They areavailable from conventional LAO processes, and have recently beenproduced intentionally in high yield and cheaply from ethylene. Pure1-Hexene is now available commercially from Fischer-Tropsch processes.Because of these diverse sources, there is advantage in using 1-hexeneas one of the feeds. The presence of 1-hexene in the LAO feed from 0 to95% is suitable. In a preferred embodiment, 1-hexene is present in thefeed in the amount of about 1 wt % or 10 wt % to about 85 wt % or less,80 wt % or less, 75 wt % or less, 67 wt % or less, 60 wt % or less, 50wt % or less, 40 wt % or less, 33 wt % or less, 30 wt % or less, 20 wt %or less, or 15 wt % or less as preferred embodiments. The same is truefor 1-octene, which can be produced selectively from 1-heptene isolatedfrom Fischer-Tropsch synthesis, or from butadiene as described in WO9210450. Other alpha-olefins such as propylene or 1-butene orcombinations thereof are also very advantageous because propylene and1-butene are readily available from refinery or from petrochemicalplants. The source of propylene can be in pure form (as in chemicalgrade propylene or as in polymer grade propylene) or in PP stream(propane-propylene stream) or other appropriate forms. The source of1-butene can be in pure form (as in chemical grade 1-butene or as inpolymer grade 1-butene) or in “BB stream” (butane-butene stream, such asRaffinate-1 or Raffinate-2 stream, as discussed, for instance, in U.S.Pat. No. 5,859,159), or other appropriate form. 1-Pentene can also beused as one of the advantaged feeds in the mixed feed. This 1-pentenecan be isolated from naphtha steam cracking unit, from other refinerysources, or from a Fischer-Tropsch synthesis process. Similar to1-hexene, in embodiments the amount of propylene, 1-butene or 1-pentenecan vary from 1 to 95% in the mixed feed, depending on the needs of theproduct properties.

The source of the LAO is advantageously from ethylene growth processes,as described in U.S. Pat. Nos. 2,889,385; 4,935,569 (and numerousreferences cited therein); U.S. Pat. No. 6,444,867; and in Chapter 3 ofLappin and Sauer, Alpha-olefins Applications Handbook, Marcel Dekker,Inc., NY 1989. The LAO made from this ethylene growth process containsonly even-number olefins. LAO containing both even- and odd-numberolefins can also be made from steam cracking or thermal cracking of wax,such as petroleum wax, Fischer-Tropsch wax, or any other readilyavailable hydrocarbon wax. LAO can also be made in a Fischer-Tropschsynthesis process, as described in U.S. Pat. No. 5,185,378 or U.S. Pat.No. 6,673,845 and references therein. LAO made directly from syngassynthesis processes, which can produce significant amounts of C₃-C₁₅alpha-olefins, containing both even- and odd-number olefins.

In an embodiment, it is advantageous to use a high quality feed withminimal inert material. However, LAO containing other inert components,including saturated hydrocarbons, internal or vinylidene olefins oraromatic diluents can also be used as feed. In this case, the LAO wouldbe reacted to give polymer and inert components will be passed throughthe reactor unaffected. The polymerization process is also a separationprocess.

Another advantaged feedstock comprises 1-butene. In certain embodiments,a mixed feed comprising from 1 wt % to about 80 wt %, preferably 5 wt %to about 75 wt %, more preferably about 25 wt % to about 75 wt % isadvantageous, particularly wherein the average carbon number of saidfeed is at least 4.1. It is particularly advantageous when the feed alsocomprises at least 20 wt % or 25 wt % to about 80 wt % or 75 wt % of atleast one alpha-olefin selected from C₈ to C₂₄, C₁₀ to C₂₄, C₁₂ to C₂₄,preferably C₁₄ to C₁₈ alpha-olefins.

It is preferred that the average carbon number of the feed is at least4.1. While the upper limit of average carbon number is not a criticalcharacteristic of the feed (and will be more naturally limited by thecharacterization of the product as an “essentially random liquidpolymer”), a useful upper limit may be given as C₂₀-C₂₄ alpha-olefins,C₁₈ or C₁₆ or C₁₄, or other preferred upper limits given herein below.Average carbon number, as used herein, refers to the average carbonnumber of the C₃ to C₃₀ alpha-olefins in the feed. Another preferredembodiment is to select a mixed feed, which may be a mixed feed asdescribed in any one of the aforementioned embodiments or as otherwisedescribed herein, having an average carbon number of between about 4.1carbon atoms and 14 carbon atoms, and more preferably from greater than5 carbon atoms to less than 12 carbon atoms, and more preferably fromgreater than 5.5 carbon atoms to less than 11 carbon atoms. The averagevalue of the carbon number (“average carbon number”) is defined as thetotal sum of the mole fraction of each alpha-olefin times the carbonnumber in the alpha-olefins (C_(av)=Σ(mole fraction)_(i)×(number ofcarbons)_(i)). There are many possible combinations to achieve thispreferred average carbon numbers of the LAO feeds. Examples of thepossible combinations are summarized in Table A. Note that in Table A,“eq. mo” feed comprises equimolar amounts of even-numbered alpha-olefinsfrom C₆ to C₁₈. All of the average carbon numbers listed in Table A arepreferred feeds, and preferred feeds also include a range of averagecarbon numbers from any lower amount listed in Table A to any higheramount listed in Table A.

A particular advantage of the present invention is that it allows forthe production of a product that closely mirrors the properties of anoligomerization process using a single feed of 1-decene without actuallyusing an appreciable amount of 1-decene or the commonly used1-decene-equivalent,

TABLE A Wt % Olefins in Feed Av. Cx* C3 C4 C5 C6 C7 C8 C9 C10 C11 C12C13 C14 C15 C16 C17 C18 C19 C20 C21 C22 C23 C24 Total C3-C23 9.7 4.5 4.54.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.54.5 4.5 100 9.0 9.1 0.0 9.1 0.0 9.1 0.0 9.1 0.0 9.1 0.0 9.1 0.0 9.1 0.09.1 0.0 9.1 0.0 9.1 0.0 9.1 0.0 100 10.5 0.0 9.1 0.0 9.1 0.0 9.1 0.0 9.10.0 9.1 0.0 9.1 0.0 9.1 0.0 9.1 0.0 9.1 0.0 9.1 0.0 9.1 100 9.9 7.1 0.07.1 0.0 7.1 0.0 7.1 7.1 7.1 0.0 7.1 0.0 7.1 0.0 7.1 0.0 0.0 7.1 7.1 7.17.1 7.1 100 C6-C18 10.7 0.0 0.0 0.0 7.7 7.7 7.7 7.7 7.7 7.7 7.7 7.7 7.77.7 7.7 7.7 7.7 0.0 0.0 0.0 0.0 0.0 0.0 100 10.5 0.0 0.0 0.0 14.3 0.014.3 0.0 14.3 0.0 14.3 0.0 14.3 0.0 14.3 0.0 14.3 0.0 0.0 0.0 0.0 0.00.0 100 C8-C12 9.7 0.0 0.0 0.0 0.0 0.0 33.3 0.0 33.3 0.0 33.3 0.0 0.00.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 100 C6-C14 9.2 0.0 0.0 0.0 20.00.0 20.0 0.0 20.0 0.0 20.0 0.0 20.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.00.0 100 C6-C16 9.9 0.0 0.0 0.0 16.7 0.0 16.7 0.0 16.7 0.0 16.7 0.0 16.70.0 16.7 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 100 C6-C18 10.5 0.0 0.0 0.014.3 0.0 14.3 0.0 14.3 0.0 14.3 0.0 14.3 0.0 14.3 0.0 14.3 0.0 0.0 0.00.0 0.0 0.0 100 C3 + C14 4.1 66.7 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.00.0 33.3 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 100 6.3 33.3 0.0 0.00.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 66.7 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.00.0 100 7.3 25.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 75.0 0.0 0.00.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 100 9.2 14.3 0.0 0.0 0.0 0.0 0.0 0.0 0.00.0 0.0 0.0 85.7 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 100 10.5 9.10.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 90.9 0.0 0.0 0.0 0.0 0.0 0.0 0.00.0 0.0 0.0 100 C4 + C8 4.3 0.0 85.7 0.0 0.0 0.0 14.3 0.0 0.0 0.0 0.00.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 100 5.3 0.0 50.0 0.0 0.00.0 50.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0100 C4 + C10 5.7 0.0 50.0 0.0 0.0 0.0 0.0 0.0 50.0 0.0 0.0 0.0 0.0 0.00.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 100 C4 + C12 4.5 0.0 83.3 0.0 0.00.0 0.0 0.0 0.0 0.0 16.7 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0100 6.0 0.0 50.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 50.0 0.0 0.0 0.0 0.0 0.00.0 0.0 0.0 0.0 0.0 0.0 0.0 100 8.6 0.0 20.0 0.0 0.0 0.0 0.0 0.0 0.0 0.080.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 100 9.8 0.0 11.10.0 0.0 0.0 0.0 0.0 0.0 0.0 88.9 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.00.0 0.0 100 10.4 0.0 7.7 0.0 0.0 0.0 0.0 0.0 0.0 0.0 92.3 0.0 0.0 0.00.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 100 10.7 0.0 5.9 0.0 0.0 0.0 0.0 0.00.0 0.0 94.1 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 100 C4 +C14 4.7 0.0 80.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 20.0 0.0 0.0 0.00.0 0.0 0.0 0.0 0.0 0.0 0.0 100 6.2 0.0 50.0 0.0 0.0 0.0 0.0 0.0 0.0 0.00.0 0.0 50.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 100 7.6 0.0 33.30.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 66.7 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.00.0 0.0 100 9.3 0.0 20.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 80.0 0.00.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 100 7.6 0.0 33.3 0.0 0.0 0.0 0.0 0.00.0 0.0 0.0 0.0 66.7 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 100 11.00.0 11.1 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 88.9 0.0 0.0 0.0 0.0 0.00.0 0.0 0.0 0.0 0.0 100 12.2 0.0 5.9 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.094.1 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 100 C4 + C16 8.0 0.0 33.30.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 66.7 0.0 0.0 0.0 0.0 0.0 0.00.0 0.0 100 10.0 0.0 20.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.080.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 100 C4 + C18 6.5 0.0 50.0 0.0 0.00.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 50.0 0.0 0.0 0.0 0.0 0.0 0.0100 9.6 0.0 25.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.075.0 0.0 0.0 0.0 0.0 0.0 0.0 100 12.0 0.0 14.3 0.0 0.0 0.0 0.0 0.0 0.00.0 0.0 0.0 0.0 0.0 0.0 0.0 85.7 0.0 0.0 0.0 0.0 0.0 0.0 100 C3,4,12 4.533.3 33.3 0.0 0.0 0.0 0.0 0.0 0.0 0.0 33.3 0.0 0.0 0.0 0.0 0.0 0.0 0.00.0 0.0 0.0 0.0 0.0 100 6.5 16.7 16.7 0.0 0.0 0.0 0.0 0.0 0.0 0.0 66.70.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 100 8.0 10.0 10.0 0.00.0 0.0 0.0 0.0 0.0 0.0 80.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.00.0 100 9.4 5.6 5.6 0.0 0.0 0.0 0.0 0.0 0.0 0.0 88.9 0.0 0.0 0.0 0.0 0.00.0 0.0 0.0 0.0 0.0 0.0 0.0 100 C3,4,14 4.0 40.0 40.0 0.0 0.0 0.0 0.00.0 0.0 0.0 0.0 0.0 20.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 100 4.633.3 33.3 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 33.3 0.0 0.0 0.0 0.0 0.00.0 0.0 0.0 0.0 0.0 100 6.9 16.7 16.7 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.00.0 66.7 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 100 9.7 7.1 7.1 0.0 0.00.0 0.0 0.0 0.0 0.0 0.0 0.0 85.7 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0100 C3,4,12,14 9.8 6.7 6.7 0.0 0.0 0.0 0.0 0.0 0.0 0.0 6.7 0.0 80.0 0.00.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 100 C3,4,5,14 4.7 25.0 25.0 25.0 0.00.0 0.0 0.0 0.0 0.0 0.0 0.0 25.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0100 6.5 14.3 14.3 14.3 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 57.1 0.0 0.0 0.00.0 0.0 0.0 0.0 0.0 0.0 0.0 100 9.1 6.7 6.7 6.7 0.0 0.0 0.0 0.0 0.0 0.00.0 0.0 80.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 100 10.8 3.7 3.73.7 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 88.9 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.00.0 0.0 100 C3,4,5,12,14 10.8 3.6 3.6 3.6 0.0 0.0 0.0 0.0 0.0 0.0 3.60.0 85.7 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 100 C4,5,6,14 5.8 0.025.0 25.0 25.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 25.0 0.0 0.0 0.0 0.0 0.0 0.00.0 0.0 0.0 0.0 100 7.8 0.0 14.3 14.3 14.3 0.0 0.0 0.0 0.0 0.0 0.0 0.057.1 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 100 10.2 0.0 6.7 6.7 6.70.0 0.0 0.0 0.0 0.0 0.0 0.0 80.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0100 11.6 0.0 3.7 3.7 3.7 0.0 0.0 0.0 0.0 0.0 0.0 0.0 88.9 0.0 0.0 0.00.0 0.0 0.0 0.0 0.0 0.0 0.0 100 C5,6,8,10,12,14,16 7.5 0.0 0.0 9.1 45.50.0 9.1 0.0 9.1 0.0 9.1 0.0 9.1 0.0 9.1 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0100 8.7 0.0 0.0 14.3 14.3 0.0 14.3 0.0 14.3 0.0 14.3 0.0 14.3 0.0 14.30.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 100 C6,12 8.0 0.0 0.0 0.0 50.0 0.0 0.00.0 0.0 0.0 50.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 100 9.00.0 0.0 0.0 33.3 0.0 0.0 0.0 0.0 0.0 66.7 0.0 0.0 0.0 0.0 0.0 0.0 0.00.0 0.0 0.0 0.0 0.0 100 10.0 0.0 0.0 0.0 20.0 0.0 0.0 0.0 0.0 0.0 80.00.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 100 10.8 0.0 0.0 0.011.1 0.0 0.0 0.0 0.0 0.0 88.9 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.00.0 0.0 100 11.1 0.0 0.0 0.0 7.7 0.0 0.0 0.0 0.0 0.0 92.3 0.0 0.0 0.00.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 100 C6,14 6.4 0.0 0.0 0.0 88.9 0.00.0 0.0 0.0 0.0 0.0 0.0 11.1 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 1008.4 0.0 0.0 0.0 50.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 50.0 0.0 0.0 0.0 0.00.0 0.0 0.0 0.0 0.0 0.0 100 9.7 0.0 0.0 0.0 33.3 0.0 0.0 0.0 0.0 0.0 0.00.0 66.7 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 100 11.1 0.0 0.0 0.020.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 80.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.00.0 0.0 100 12.2 0.0 0.0 0.0 11.1 0.0 0.0 0.0 0.0 0.0 0.0 0.0 88.9 0.00.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 100 12.7 0.0 0.0 0.0 7.7 0.0 0.0 0.00.0 0.0 0.0 0.0 92.3 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 100C6,12,14 7.1 0.0 0.0 0.0 71.4 0.0 0.0 0.0 0.0 0.0 14.3 0.0 14.3 0.0 0.00.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 100 9.3 0.0 0.0 0.0 33.3 0.0 0.0 0.0 0.00.0 33.3 0.0 33.3 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 100 10.5 0.00.0 0.0 20.0 0.0 0.0 0.0 0.0 0.0 40.0 0.0 40.0 0.0 0.0 0.0 0.0 0.0 0.00.0 0.0 0.0 0.0 100 11.5 0.0 0.0 0.0 11.1 0.0 0.0 0.0 0.0 0.0 44.4 0.044.4 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 100 12.1 0.0 0.0 0.0 5.90.0 0.0 0.0 0.0 0.0 47.1 0.0 47.1 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.00.0 100 12.4 0.0 0.0 0.0 4.0 0.0 0.0 0.0 0.0 0.0 48.0 0.0 48.0 0.0 0.00.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 100 11.3 0.0 0.0 0.0 7.1 0.0 0.0 0.0 0.00.0 85.7 0.0 7.1 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 100 11.3 0.00.0 0.0 9.1 0.0 0.0 0.0 0.0 0.0 72.7 0.0 18.2 0.0 0.0 0.0 0.0 0.0 0.00.0 0.0 0.0 0.0 100 11.5 0.0 0.0 0.0 11.1 0.0 0.0 0.0 0.0 0.0 44.4 0.044.4 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 100 12.2 0.0 0.0 0.0 9.10.0 0.0 0.0 0.0 0.0 18.2 0.0 72.7 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.00.0 100 12.6 0.0 0.0 0.0 7.1 0.0 0.0 0.0 0.0 0.0 7.1 0.0 85.7 0.0 0.00.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 100 C6,10,12,14 9.5 0.0 0.0 0.0 25.0 0.00.0 0.0 25.0 0.0 25.0 0.0 25.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0100 10.4 0.0 0.0 0.0 14.3 0.0 0.0 0.0 28.6 0.0 28.6 0.0 28.6 0.0 0.0 0.00.0 0.0 0.0 0.0 0.0 0.0 0.0 100 11.0 0.0 0.0 0.0 7.7 0.0 0.0 0.0 30.80.0 30.8 0.0 30.8 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 100 11.3 0.00.0 0.0 4.0 0.0 0.0 0.0 32.0 0.0 32.0 0.0 32.0 0.0 0.0 0.0 0.0 0.0 0.00.0 0.0 0.0 0.0 100 7.6 0.0 0.0 0.0 57.1 0.0 0.0 0.0 14.3 0.0 14.3 0.014.3 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 100 7.2 0.0 0.0 0.0 66.70.0 0.0 0.0 11.1 0.0 11.1 0.0 11.1 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.00.0 100 6.7 0.0 0.0 0.0 80.0 0.0 0.0 0.0 6.7 0.0 6.7 0.0 6.7 0.0 0.0 0.00.0 0.0 0.0 0.0 0.0 0.0 0.0 100 7.0 0.0 0.0 0.0 75.0 0.0 0.0 0.0 0.0 0.06.3 0.0 18.8 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 100 9.7 0.0 0.0 0.027.3 0.0 0.0 0.0 9.1 0.0 27.3 0.0 36.4 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.00.0 0.0 100 10.4 0.0 0.0 0.0 25.0 0.0 0.0 0.0 0.0 0.0 25.0 0.0 25.0 0.025.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 100 8.2 0.0 0.0 0.0 50.0 0.0 0.00.0 0.0 0.0 25.0 0.0 25.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 1007.4 0.0 0.0 0.0 57.1 0.0 0.0 0.0 28.6 0.0 7.1 0.0 7.1 0.0 0.0 0.0 0.00.0 0.0 0.0 0.0 0.0 0.0 100 eq mo 12.0 0.0 0.0 0.0 7.1 0.0 9.5 0.0 11.90.0 14.3 0.0 16.7 0.0 19.1 0.0 21.4 0.0 0.0 0.0 0.0 0.0 0.0 100 C2growth 9.3 0.0 0.0 0.0 18.4 0.0 22.3 0.0 21.6 0.0 16.8 0.0 10.4 0.0 6.40.0 4.0 0.0 0.0 0.0 0.0 0.0 0.0 100 wax crack 10.4 0.0 0.0 5.1 6.1 6.17.2 7.7 8.0 7.8 6.1 7.1 5.9 7.1 5.6 5.9 5.0 5.1 4.1 0.0 0.0 0.0 0.0 100wax crack 10.0 0.0 0.0 5.6 6.8 6.8 7.9 8.5 8.8 8.6 6.8 7.8 6.5 7.8 6.26.5 5.5 0.0 0.0 0.0 0.0 0.0 0.0 100 wax crack 12.5 0.0 0.0 0.0 0.0 0.00.0 11.6 12.1 11.7 9.3 10.7 9.0 10.7 8.5 9.0 7.6 0.0 0.0 0.0 0.0 0.0 0.0100 wax crack 11.4 0.0 0.0 0.0 0.0 0.0 0.0 16.1 16.7 16.3 12.9 14.8 12.46.4 4.3 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 100 wax crack 10.9 0.0 0.0 0.00.0 0.0 0.0 19.8 20.6 20.1 15.8 13.2 10.6 0.0 0.0 0.0 0.0 0.0 0.0 0.00.0 0.0 0.0 100which often contains about equal molar of 1-octene and 1-dodecene. Thus,in an embodiment, the feed used in the present invention does notcontain 1-decene, or contains 1-decene in an amount less than about 1 wt%, or less than about 5 wt %, or less than about 10 wt %, or less thanabout 20 wt %, or less than 30%, or less than 50%, or less than 60%, orless than 70%, and also an embodiment wherein the feed from one of thesepreferred embodiments not having an appreciable amount of 1-decene isused to produce a product having substantially similar properties as aproduct produced using a feed comprising substantially all 1-decene, or90 wt % 1-decene. Preferred embodiments include feeds where any one of1-octene, 1-decene, and 1-dodecene is less then 70%, 50 wt %, or 40 wt%, or 33 wt %, or 30 wt %, or 25 wt %, or 20 wt %, or 10 wt %, or 5 wt%, and/or wherein the total of 1-octene, 1-decene, and 1-dodecene ispresent in the aforementioned amounts.

One of the advantages of the present invention is that a feed may betaken directly from another process without laborious, time-consuming,and/or expensive isolation of one or more monomers. Thus, for example, apreferred embodiment is a feed used directly, with minimum isolation,from an ethylene growth process. Usually, LAO processes produce C₆ toC₂₀ LAO with small amounts of C₂₀₊ LAO. In typical production processes,each individual C₆ to C₁₈ LAO is isolated from the crude mixture bycareful fractionation. Usually each LAO has it unique application. Thisfractionation step adds cost and complexicity to the LAO production. Inthe present invention, the whole range of C₄ to C₂₀₊ LAO directly fromthe oligomerization process can be used as feed, with only a separationof the light gases. There is no need to separate each individualfraction. Or, a wide range of LAO from C₆ to C₂₀ distilled in onefraction to separate it from the heavy C₂₀₊ bottom can be used as feedin this invention. Or, a wide range of LAO from C₆ to C₁₈ distilled inone fraction from the remaining heavy LAOs can be used as feed. And soforth for any range LAO desired. This whole range or wide range LAOwhich requires no or minimum or simple isolation is a superior feed forthis invention. To be able to use this whole range or wide range LAOoffers economic advantage and furthermore, the product properties aresuperior.

Under certain reaction conditions, ethylene may be used as a “growthreagent” to produce alpha-olefins which are low molecular weightpolymers (oligomers) of the growth reagent. Such reactions aredescribed, for instance, in U.S. Pat. Nos. 2,889,385; 4,935,569 (andnumerous references cited therein); U.S. Pat. No. 6,444,867; and inChapter 3 of Lappin and Sauer, Alpha-olefins Applications Handbook,Marcel Dekker, Inc., NY 1989. The entire mixture of olefins produced byone of such processes, comprising, for example, nine differentalpha-olefin oligomers of ethylene having from 4 to 20 carbon atoms, maybe used directly in the process of the present invention with minimumisolation of the bulk of the alpha-olefins but without the necessity ofseparating the each individual oligomer. Mixtures of linearalpha-olefins (LAO) produced by other processes such as steam/thermalcracking of petroleum-based slack wax or more desirably from thesteam/thermal cracking of wax derived from Fischer-Tropsch (FT)synthesis as described in the paper “Gas-to-Liquids Technology ProvidesNew Hope for Remote Fields” published in Lubricant World, October 2000,page 30. By properly selecting the cracking conditions, alpha-olefinsranging from C₅ to C₁₈ can be produced in high yields, as described inU.S. Pat. Nos. 5,136,118; 5,146,002; and 5,208,403. In all thesecracking processes, the wax derived from GTL process is the mostdesirable feed because of its high purity, lack of sulfur, nitrogen orother heteroatoms, and its low aromatics, naphthenics, and branchedparaffins, content.

Mixtures of LAOs can also be produced directly from Fischer-Tropschsynthesis using special catalysts, usually cobalt or iron based FTcatalysts, in combination with a synthesis gas with a low H₂/CO ratio.The mixture of alpha-olefins with only even carbon numbers or with bothodd and even carbon numbers can be used with minimum separation as feedfor this invention, or can be separated into different fractions.Fractions with no other special use can be used as feed in thisinvention process to yield high quality synthetic fluids. This approachprovides a method to optimize total LAO value. Examples of the feedcompositions are summarized in Table A. In many cases, the preferredfeeds are chosen from C₃- to C₇ alpha-olefins in combination withanother olefin or olefins chosen from C₁₂ to C₂₀ alpha-olefins. Thisapproach leaves out the C₈ and C₁₀ LAOs or uses only minimum amounts ofthem. The C₈ and C₁₀ LAOs are usually in high demand from otherapplications, such as for use as co-monomers for polyethylene plasticsynthesis or used in BF₃ or AlCl₃-based oligomerization processes, whichprefer 1-decene as feed. Or if C₈ and C₁₀ alpha-olefins are available,then they can be added as part of the feed.

In addition to LAO used in this process, other alpha-olefins containingbranches that are at least two carbons away from the olefinic doublebonds can also be used as one of the mixture components. Examples ofthese alpha-olefins include 4-methyl-1-pentene, or other slightlybranched alpha-olefins produced from Fischer-Tropsch synthesis processor from wax-cracking process. These slightly branched alpha-olefins canbe used together with the LAOs described above as feeds.

Polymerization Catalyst System

This improved process employs a catalyst system comprising a metallocenecompound (Formula 1, below) together with an activator such as anon-coordinating anion (NCA) activator (Formula 2, below, is oneexample) or methylaluminoxane (MAO) (Formula 3, below).

The term “catalyst system” is defined herein to mean a catalystprecursor/activator pair, such as a metallocene/activator pair. When“catalyst system” is used to describe such a pair before activation, itmeans the unactivated catalyst (precatalyst) together with an activatorand, optionally, a co-activator (such as a trialkyl aluminum compound).When it is used to describe such a pair after activation, it means theactivated catalyst and the activator or other charge-balancing moiety.Furthermore, this activated “catalyst system” may optionally comprisethe co-activator and/or other charge-balancing moiety.

The metallocene is selected from one or more compounds according toFormula 1, above. In Formula 1, M is selected from Group 4 transitionmetals, preferably zirconium (Zr), hafnium (Hf) and titanium (Ti), L1and L2 are independently selected from cyclopentadienyl (“Cp”), indenyl,and fluorenyl, which may be substituted or unsubstituted, and which maybe partially hydrogenated, A is an optional bridging group which ifpresent, in preferred embodiments is selected from dialkylsilyl,dialkylmethyl, ethenyl (—CH₂—CH₂—), alkylethenyl (—CR₂—CR₂—), wherealkyl can be independently hydrogen radical, C₁ to C₁₆ alkyl radical orphenyl, tolyl, xylyl radical and the like, and wherein each of the two Xgroups, X^(a) and X^(b), are independently selected from halides, OR (Ris an alkyl group, preferably selected from C₁ to C₅ straight orbranched chain alkyl groups), hydrogen, C₁ to C₁₆ alkyl or aryl groups,haloalkyl, and the like. Usually relatively more highly substitutedmetallocenes give higher catalyst productivity and wider productviscosity ranges and are thus often more preferred.

In using the terms “substituted or unsubstituted cyclopentadienylligand”, “substituted or unsubstituted indenyl ligand”, and “substitutedor unsubstituted tetrahydroindenyl ligand”, “substituted orunsubstituted fluorenyl ligand”, and “substituted or unsubstitutedtetrahydrofluorenyl or octahydrofluorenyl ligand” the substitution tothe aforementioned ligand may be hydrocarbyl, substituted hydrocarbyl,halocarbyl, substituted halocarbyl, silylcarbyl, or germylcarbyl. Thesubstitution may also be within the ring giving heterocyclopentadienylligands, heteroindenyl ligands or heterotetrahydoindenyl ligands, eachof which can additional be substituted or unsubstituted.

For purposes of this invention and the claims thereto the terms“hydrocarbyl radical,” “hydrocarbyl” and hydrocarbyl group” are usedinterchangeably throughout this document. Likewise the terms “group”,“radical” and “substituent” are also used interchangeably in thisdocument. For purposes of this disclosure, “hydrocarbyl radical” isdefined to be C₁-C₁₀₀ radicals, that may be linear, branched, or cyclic,and when cyclic, aromatic or non-aromatic, and include substitutedhydrocarbyl radicals, halocarbyl radicals, and substituted halocarbylradicals, silylcarbyl radicals, and germylcarbyl radicals as these termsare defined below.

Substituted hydrocarbyl radicals are radicals in which at least onehydrogen atom has been substituted with at least one functional groupsuch as NR*₂, OR*, SeR*, TeR*, PR*₂, AsR*₂, SbR*₂, SR*, BR*₂, SiR*₃,GeR*₃, SnR*₃, PbR*₃ and the like or where at least one non-hydrocarbonatom or group has been inserted within the hydrocarbyl radical, such as—O—, —S—, —Se—, —Te—, —N(R*)—, ═N—, —P(R*)—, ═P—, —As(R*)—, ═As—,—Sb(R*)—, ═Sb—, —B(R*)—, ═B—, —Si(R*)₂—, —Ge(R*)₂—, —Sn(R*)₂—, —Pb(R*)₂—and the like, where R* is independently a hydrocarbyl or halocarbylradical, and two or more R* may join together to form a substituted orunsubstituted saturated, partially unsaturated or aromatic cyclic orpolycyclic ring structure.

Halocarbyl radicals are radicals in which one or more hydrocarbylhydrogen atoms have been substituted with at least one halogen (e.g. F,Cl, Br, I) or halogen-containing group (e.g. CF₃).

Substituted halocarbyl radicals are radicals in which at least onehalocarbyl hydrogen or halogen atom has been substituted with at leastone functional group such as NR*₂, OR*, SeR*, TeR*, PR*₂, AsR*₂, SbR*₂,SR*, BR*₂, SiR*₃, GeR*₃, SnR*₃, PbR*₃ and the like or where at least onenon-carbon atom or group has been inserted within the halocarbyl radicalsuch as —O—, —S—, —Se—, —Te—, —N(R*)—, ═N—, —P(R*)—, ═P—, —As(R*)—,═As—, —Sb(R*)—, ═Sb—, —B(R*)—, ═B—, —Si(R*)₂—, —Ge(R*)₂—, —Sn(R*)₂—,—Pb(R*)₂— and the like, where R* is independently a hydrocarbyl orhalocarbyl radical provided that at least one halogen atom remains onthe original halocarbyl radical. Additionally, two or more R* may jointogether to form a substituted or unsubstituted saturated, partiallyunsaturated or aromatic cyclic or polycyclic ring structure.

Silylcarbyl radicals (also called silylcarbyls) are groups in which thesilyl functionality is bonded directly to the indicated atom or atoms.Examples include SiH₃, SiH₂R*, SiHR*₂, SiR*₃, SiH₂(OR*), SiH(OR*)₂,Si(OR*)₃, SiH₂(NR*₂), SiH(NR*₂)₂, Si(NR*₂)₃, and the like where R* isindependently a hydrocarbyl or halocarbyl radical and two or more R* mayjoin together to form a substituted or unsubstituted saturated,partially unsaturated or aromatic cyclic or polycyclic ring structure.

Germylcarbyl radicals (also called germylcarbyls) are groups in whichthe germyl functionality is bonded directly to the indicated atom oratoms. Examples include GeH₃, GeH₂R*, GeHR*₂, GeR*₃, GeH₂(OR*),GeH(OR*)₂, Ge(OR*)₃, GeH₂(NR*₂), GeH(NR*₂)₂, Ge(NR*₂)₃, and the likewhere R* is independently a hydrocarbyl or halocarbyl radical and two ormore R* may join together to form a substituted or unsubstitutedsaturated, partially unsaturated or aromatic cyclic or polycyclic ringstructure.

Polar radicals or polar groups are groups in which the heteroatomfunctionality is bonded directly to the indicated atom or atoms. Theyinclude heteroatoms of groups 1-17 of the Periodic Table either alone orconnected to other elements by covalent or other interactions such asionic, van der Waals forces, or hydrogen bonding. Examples of functionalheteroatom containing groups include carboxylic acid, acid halide,carboxylic ester, carboxylic salt, carboxylic anhydride, aldehyde andtheir chalcogen (Group 14) analogues, alcohol and phenol, ether,peroxide and hydroperoxide, carboxylic amide, hydrazide and imide,amidine and other nitrogen analogues of amides, nitrile, amine andimine, azo, nitro, other nitrogen compounds, sulfur acids, seleniumacids, thiols, sulfides, sulfoxides, sulfones, phosphines, phosphates,other phosphorus compounds, silanes, boranes, borates, alanes,aluminates. Functional groups may also be taken broadly to includeorganic polymer supports or inorganic support material such as alumina,and silica. Preferred examples of polar groups include NR*₂, OR*, SeR*,TeR*, PR*₂, AsR*₂, SbR*₂, SR*, BR*₂, SnR*₃, PbR*₃ and the like where R*is independently a hydrocarbyl, substituted hydrocarbyl, halocarbyl orsubstituted halocarbyl radical as defined above and two R* may jointogether to form a substituted or unsubstituted saturated, partiallyunsaturated or aromatic cyclic or polycyclic ring structure.

In some embodiments, the hydrocarbyl radical is independently selectedfrom methyl, ethyl, ethenyl and isomers of propyl, butyl, pentyl, hexyl,heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl,pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl,heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl,heptacosyl, octacosyl, nonacosyl, triacontyl, propenyl, butenyl,pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl,dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl,heptadecenyl, octadecenyl, nonadecenyl, eicosenyl, heneicosenyl,docosenyl, tricosenyl, tetracosenyl, pentacosenyl, hexacosenyl,heptacosenyl, octacosenyl, nonacosenyl, triacontenyl, propynyl, butynyl,pentynyl, hexynyl, heptynyl, octynyl, nonynyl, decynyl, undecynyl,dodecynyl, tridecynyl, tetradecynyl, pentadecynyl, hexadecynyl,heptadecynyl, octadecynyl, nonadecynyl, eicosynyl, heneicosynyl,docosynyl, tricosynyl, tetracosynyl, pentacosynyl, hexacosynyl,heptacosynyl, octacosynyl, nonacosynyl, triacontynyl, butadienyl,pentadienyl, hexadienyl, heptadienyl, octadienyl, nonadienyl, anddecadienyl. Also included are isomers of saturated, partiallyunsaturated and aromatic cyclic and polycyclic structures wherein theradical may additionally be subjected to the types of substitutionsdescribed above. Examples include phenyl, methylphenyl, dimethylphenyl,ethylphenyl, diethylphenyl, propylphenyl, dipropylphenyl, benzyl,methylbenzyl, naphthyl, anthracenyl, cyclopentyl, cyclopentenyl,cyclohexyl, cyclohexenyl, methylcyclohexyl, cycloheptyl, cycloheptenyl,norbornyl, norbornenyl, adamantyl and the like. For this disclosure,when a radical is listed, it indicates that radical type and all otherradicals formed when that radical type is subjected to the substitutionsdefined above. Alkyl, alkenyl and alkynyl radicals listed include allisomers including where appropriate cyclic isomers, for example, butylincludes n-butyl, 2-methylpropyl, 1-methylpropyl, tert-butyl, andcyclobutyl (and analogous substituted cyclopropyls); pentyl includesn-pentyl, cyclopentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl,1-ethylpropyl, and neopentyl (and analogous substituted cyclobutyls andcyclopropyls); butenyl includes E and Z forms of 1-butenyl, 2-butenyl,3-butenyl, 1-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-1-propenyland 2-methyl-2-propenyl (and cyclobutenyls and cyclopropenyls). Cycliccompound having substitutions include all isomer forms, for example,methylphenyl would include ortho-methylphenyl, meta-methylphenyl andpara-methylphenyl; dimethylphenyl would include 2,3-dimethylphenyl,2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-diphenylmethyl,3,4-dimethylphenyl, and 3,5-dimethylphenyl.

Examples of cyclopentadienyl and indenyl ligands are illustrated belowas anionic ligands. The ring numbering scheme is also illustrated.

A similar numbering and nomenclature scheme is used for heteroindenyl asillustrated below where Z and Q independently represent the heteroatomsO, S, Se, or Te, or heteroatom groups, NR′, PR′, AsR′, or SbR′ where R′is hydrogen, or a hydrocarbyl, substituted hydrocarbyl, halocarbyl,substituted halocarbyl, silylcarbyl, or germylcarbyl substituent. Thenumber scheme shown below is for heteroindenyl ligands that are bridgedto another ligand via a bridging group.

A similar numbering and nomenclature scheme is used forheterocyclopentadienyl rings as illustrated below where G and Jindependently represent the heteroatoms N, P, As, Sb or B. For theseligands when bridged to another ligand via a bridging group, the oneposition is usually chosen to be the ring carbon position where theligand is bonded to the bridging group, hence a numbering scheme is notillustrated below.

Depending on the position of the bridging ligand, the numbering for thefollowing ligands will change; 1,3 and 1,2 are only used in this case toillustrate the position of the heteroatoms relative to one another.

A “ring heteroatom” is a heteroatom that is within a cyclic ringstructure. A “heteroatom substituent” is heteroatom containing groupthat is directly bonded to a ring structure through the heteroatom. A“bridging heteroatom substituent” is a heteroatom or heteroatom groupthat is directly bonded to two different ring structures through theheteroatom. The terms “ring heteroatom”, “heteroatom substituent”, and“bridging heteroatom substituent” are illustrated below where Z and R′are as defined above. It should be noted that a “heteroatom substituent”can be a “bridging heteroatom substituent” when R′ is additionallydefined as the ligand “A”.

A “ring carbon atom” is a carbon atom that is part of a cyclic ringstructure. By this definition, an indenyl ligand has nine ring carbonatoms; a cyclopentadienyl ligand has five ring carbon atoms. Transitionmetal compounds have symmetry elements and belong to symmetry groups.These elements and groups are well established and can be referencedfrom Chemical Applications of Group Theory (2nd Edition) by F. AlbertCotton, Wiley-Interscience, 1971. Pseudo-symmetry, such as a pseudoC₂-axis of symmetry refers to the same symmetry operation, however, thesubstituents on the ligand frame do not need to be identical, but ofsimilar size and steric bulk. Substituents of similar size are typicallywithin 4 atoms of each other, and of similar shape. For example, methyl,ethyl, n-propyl, n-butyl and iso-butyl substituents (e.g. C₁-C₄ primarybonded substituents) would be considered of similar size and stericbulk. Likewise, iso-propyl, sec-butyl, 1-methylbutyl, 1-ethylbutyl and1-methylpentyl substituents (e.g. C₃-C₆ secondary bonded substituents)would be considered of similar size and steric bulk. Tert-butyl,1,1-dimethylpropyl, 1,1-dimethylbutyl, 1,1-dimethylpentyl and1-ethyl-1-methylpropyl (e.g. C₄-C₇ tertiary bonded substituents) wouldbe considered of similar size and steric bulk. Phenyl, tolyl, xylyl, andmesityl substituents (C₆-C₉ aryl substituents) would be considered ofsimilar size and steric bulk. Additionally, the bridging substituents ofa compound with a pseudo C₂-axis of symmetry do not have to be similarat all since they are far removed from the active site of the catalyst.Therefore, a compound with a pseudo C₂-axis of symmetry could have forexample, a Me₂Si, MeEtSi or MePhSi bridging ligand, and still beconsidered to have a pseudo C₂-axis of symmetry given the appropriateremaining ligand structure.

For purposes of this disclosure, the term oligomer refers tocompositions having 2-75 mer units and the term polymer refers tocompositions having 76 or more mer units. A mer is defined as a unit ofan oligomer or polymer that originally corresponded to the olefin(s)used in the oligomerization or polymerization reaction. For example, themer of polydecene would be decene.

The metallocene compounds (pre-catalysts), useful herein are preferablycyclopentadienyl derivatives of titanium, zirconium and hafnium. Ingeneral, useful titanocenes, zirconocenes and hafnocenes may berepresented by the following formulae 4 and 5:

(Cp-A′-Cp*)MX^(a)X^(b)  (4)

(CpCp*)MX^(a)X^(b)  (5)

wherein:M is the metal center, and is a Group 4 metal preferably Titanium,zirconium or hafnium, preferably zirconium or hafnium; Cp and Cp* arethe same or different cyclopentadienyl rings substituted with from zeroto four or five substituent groups S″, each substituent group S″ being,independently, a radical group which is a hydrocarbyl, substitutedhydrocarbyl, halocarbyl, substituted halocarbyl, silylcarbyl orgermylcarbyl, or Cp and Cp* are the same or different cyclopentadienylrings in which any two adjacent S″ groups are joined to form asubstituted or unsubstituted, saturated, partially unsaturated, oraromatic cyclic or polycyclic substituent;A′ is a bridging group;X^(a) and X^(b) are, independently, hydride radicals, hydrocarbylradicals, substituted hydrocarbyl radicals, halocarbyl radicals,substituted halocarbyl radicals, silylcarbyl radicals, substitutedsilylcarbyl radicals, germylcarbyl radicals, or substituted germylcarbylradicals; or both X are joined and bound to the metal atom to form ametallacycle ring containing from about 3 to about 20 carbon atoms; orboth together can be an olefin, diolefin or aryne ligand; or whenLewis-acid activators, such as methylaluminoxane or trialkylaluminum ortrialkylboron, etc., which are capable of donating a hydrocarbyl ligandas described above to the transition metal component, are used, both Xmay, independently, be a halogen, alkoxide, aryloxide, amide, phosphideor other univalent anionic ligand or both X can also be joined to form aanionic chelating ligand.

In a preferred embodiment the metallocene is racemic which means in apreferred embodiment, that the compounds represented by formula (4) haveno plane of symmetry containing the metal center, M; and have a C₂-axisof symmetry or pseudo C₂-axis of symmetry through the metal center.Preferably in the racemic metallocenes represented by formula (1) A′ isselected from R′₂C, R′₂Si, R′₂Ge, R′₂CCR′₂, R′₂CCR′₂CR′₂,R′₂CCR′₂CR′₂CR′₂, R′C═CR′, R′C═CR′ CR′₂, R′₂CCR′═CR′CR′₂,R′C═CR′CR′═CR′, R′C═CR′CR′₂CR′₂, R′₂CSiR′₂, R′₂SiSiR′₂, R′₂CSiR′₂CR′₂,R′₂SiCR′₂SiR′₂, R′C═CR′ SiR′₂, R′₂CGeR′₂, R′₂GeGeR′₂, R′₂CGeR′₂CR′₂,R′₂GeCR′₂GeR′₂, R′₂SiGeR′₂, R′C═CR′GeR′₂, R′B, R′₂C—BR′, R′₂C—BR′—CR′₂,R′N, R′P, O, S, Se, R′₂C—O—CR′₂, R′₂CR′₂C—O—CR′₂CR′₂, R′₂C—O—CR′₂CR′₂,R′₂C—O—CR′═CR′, R′₂C—S—CR′₂, R′₂CR′₂C—S—CR′₂CR′₂, R′₂C—S—CR′₂CR′₂,R′₂C—S—CR′═CR′, R′₂C—Se—CR′₂, R′₂CR′₂C—Se—CR′₂CR′₂, R′₂C—Se—CR′₂CR′₂,R′₂C—Se—CR′═CR′, R′₂C—N═CR′, R′₂C—NR′—CR′₂, R′₂C—NR′—CR′₂CR′₂,R′₂C—NR′—CR′═CR′, R′₂CR′₂C—NR′—CR′₂CR′₂, R′₂C—P═CR′, and R′₂C—PR′—CR′₂and when Cp is different than Cp*, R′ is a C₁-C₅-containing hydrocarbyl,substituted hydrocarbyl, halocarbyl, substituted halocarbyl, silylcarbylor germylcarbyl substituent, and when Cp is the same as Cp*, R′ is aC₁-C₂₀-containing hydrocarbyl, substituted hydrocarbyl, halocarbyl,substituted halocarbyl, silylcarbyl or germylcarbyl substituent andoptionally two or more adjacent R′ may join to form a substituted orunsubstituted, saturated, partially unsaturated, cyclic or polycyclicsubstituent. Similarly, C₁ metallocenes can also be used for thisinvention. All these catalysts usually produce polyalpha-olefins withhigh degree of isotacticity or highly isotactic polymers. See J. Am.Chem. Soc. 1988, 110, 6225 for a review of the effect of catalyststructure on polymer tacticity, In addition to catalyst structures, thedegree of isotacticity depends on other factors, such as catalystpurity, ligand types, reaction conditions, etc. The polymers withvarious degrees of tacticity are useful as synthetic lube base stocks orfunctional fluids.

In another preferred embodiment the metallocene is the meso form whichmeans that the compounds represented by formula (4) have plane ofsymmetry containing the metal center, M. In other words, themetallocenes containing a C_(2v) symmetry are also suitable for thisapplication. This class of catalysts usually produces atacticpolyalpha-olefins. In many cases, metallocene catalysts without anybridging between the cyclopentadienyl ligands, as in formula (5), alsoproduce atactic polyalpha-olefins. In another preferred embodiment, themetallocenes with C_(s) symmetry or minor variations thereof can also beused for this invention. These types of metallocenes when activatedusually produced syndiotactic polyalpha-olefins. In the presentinvention, the polyalpha-olefins can be made from at least twoalpha-olefins mixture using any one class of the catalysts to produceisotactic, atactic or syndiotactic polymer or combinations of thesedifferent tacticities in varying amounts. The PAO products made frommixed alpha-olefin feeds and with predominantly isotactic, atactic orsyndiotactic compositions or combinations of these different tacticitiesin varying amounts all have superior VI and low temperature properties.Using mixed alpha-olefins as feeds is more advantageous than using pureolefins, especially in improving low temperature viscosities. Otherappropriate forms of catalysts which may produce combinations of thesedifferent tacticities, in a block or semi-block manner are also suitablefor this invention.

Another important characteristic of these metallocene catalysts is thatthey copolymerize the two or more alpha-olefins at comparable reactionrates. Metallocene catalysts differ from conventional Ziegler-Natta orsupported metal oxide on silica gel catalysts. These conventionalcatalysts usually polymerize smaller olefins, e.g., C₃ or C₄, muchfaster than the larger LAOs, such as C₁₂, C₁₄, etc. This is not the casefor the metallocene catalysts of the present invention, where thereactivities of C₃ and C₁₈ alpha-olefins are relatively similar. Becauseof this uniform reactivity toward all the alpha-olefin feeds, the co- orterpolymer products by metallocene are random. This randomness ofmonomer distribution is important for imparting the resultant polymerwith the desired lube basestock properties discussed earlier.

Table B depicts representative constituent moieties for the metallocenecomponents of formulas 4 and 5. The list is for illustrative purposesonly and should not be construed to be limiting in any way. A number offinal components may be formed by permuting all possible combinations ofthe constituent moieties with each other. When hydrocarbyl radicalsincluding alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl,cycloalkynyl and aromatic radicals are disclosed in this application theterm includes all isomers. For example, butyl includes n-butyl,2-methylpropyl, 1-methylpropyl, tert-butyl, and cyclobutyl; pentylincludes n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl,1-ethylpropyl, neopentyl, cyclopentyl and methylcyclobutyl; butenylincludes E and Z forms of 1-butenyl, 2-butenyl, 3-butenyl,1-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-1-propenyl and2-methyl-2-propenyl. This includes when a radical is bonded to anothergroup, for example, propylcyclopentadienyl includen-propylcyclopentadienyl, isopropylcyclopentadienyl andcyclopropylcyclopentadienyl. In general, the ligands or groupsillustrated in Table B include all isomeric forms. For example,dimethylcyclopentadienyl includes 1,2-dimethylcyclopentadienyl and1,3-dimethylcyclopentadienyl; methylindenyl includes 1-methylindenyl,2-methylindenyl, 3-methylindenyl, 4-methylindenyl, 5-methylindenyl,6-methylindenyl and 7-methylindenyl; methylethylphenyl includesortho-methylethylphenyl, meta-methylethylphenyl andpara-methylethylphenyl. Examples of specific invention catalystprecursors take the following formula where some components are listedin Table B. To illustrate members of the transition metal component,select any combination of the species listed in Tables B. Fornomenclature purposes, for the bridging group, A′, the words “silyl” and“silylene” are used interchangeably, and represent a diradical species.For the bridging group A′, “ethylene” refers to a 1,2-ethylene linkageand is distinguished from ethene-1,1-diyl. Thus, for the bridging groupA′, “ethylene” and “1,2-ethylene” are used interchangeably. Forcompounds having a bridging group, A′, the bridge position on thecyclopentadienyl-type ring is always considered the 1-position. Thenumbering scheme previous defined for the indenyl ring is used toindicate the bridge position; if a number is not specified, it isassumed that the bridge to the indenyl ligand is in the one position.

TABLE B A′ Cp, Cp* dimethylsilylene cyclopentadienyl diethylsilylenemethylcyclopentadienyl dipropylsilylene dimethylcyclopentadienyldibutylsilylene trimethylcyclopentadienyl dipentylsilylenetetramethylcyclopentadienyl dihexylsilylene ethylcyclopentadienyldiheptylsilylene diethylcyclopentadienyl dioctylsilylenepropylcyclopentadienyl dinonylsilylene dipropylcyclopentadienyldidecylsilylene butylcyclopentadienyl diundecylsilylenedibutylcyclopentadienyl didodecylsilylene pentylcyclopentadienylditridecylsilylene dipentylcyclopentadienyl ditetradecylsilylenehexylcyclopentadienyl dipentadecylsilylene dihexylcyclopentadienyldihexadecylsilylene heptylcyclopentadienyl diheptadecylsilylenediheptylcyclopentadienyl dioctadecylsilylene octylcyclopentadienyldinonadecylsilylene dioctylcyclopentadienyl dieicosylsilylenenonylcyclopentadienyl diheneicosylsilylene dinonylcyclopentadienyldidocosylsilylene decylcyclopentadienyl ditricosylsilylenedidecylcyclopentadienyl ditetracosylsilylene undecylcyclopentadienyldipentacosylsilylene dodecylcyclopentadienyl dihexacosylsilylenetridecylcyclopentadienyl diheptacosylsilylene tetradecylcyclopentadienyldioctacosylsilylene pentadecylcyclopentadienyl dinonacosylsilylenehexadecylcyclopentadienyl ditriacontylsilyleneheptadecylcyclopentadienyl dicyclohexylsilyleneoctadecylcyclopentadienyl dicyclopentylsilylenenonadecylcyclopentadienyl dicycloheptylsilylene eicosylcyclopentadienyldicyclooctylsilylene heneicosylcyclopentadienyl dicyclodecylsilylenedocosylcyclopentadienyl dicyclododecylsilylene tricosylcyclopentadienyldinapthylsilylene tetracosylcyclopentadienyl diphenylsilylenepentacosylcyclopentadienyl ditolylsilylene hexacosylcyclopentadienyldibenzylsilylene heptacosylcyclopentadienyl diphenethylsilyleneoctacosylcyclopentadienyl di(butylphenethyl)silylenenonacosylcyclopentadienyl methylethylsilylene triacontylcyclopentadienylmethylpropylsilylene cyclohexylcyclopentadienyl methylbutylsilylenephenylcyclopentadienyl methylhexylsilylene diphenylcyclopentadienylmethylphenylsilylene triphenylcyclopentadienyl ethylphenylsilylenetetraphenylcyclopentadienyl ethylpropylsilylene tolylcyclopentadineylethylbutylsilylene benzylcyclopentadienyl propylphenylsilylenephenethylcyclopentadienyl dimethylgermylenecyclohexylmethylcyclopentadienyl diethylgermylenenapthylcyclopentadienyl diphenylgermylene methylphenylcyclopentadienylmethylphenylgermylene methyltolylcyclopentadienylcyclotetramethylenesilylene methylethylcyclopentadienylcyclopentamethylenesilylene methylpropylcyclopentadienylcyclotrimethylenesilylene methylbutylcyclopentadienylcyclohexylazanediyl methylpentylcyclopentadienyl butylazanediylmethylhexylcyclopentadienyl methylazanediyl methylheptylcyclpentadienylphenylazanediyl methyloctylcyclopentadienyl perfluorophenylazanediylmethylnonylcyclopentadienyl methylphosphanediylmethyldecylcyclopentadienyl ethylphosphanediyl vinylcyclopentadienylpropylphosphanediyl propenylcyclopentadienyl butylphosphanediylbutenylcyclopentadienyl cyclohexylphosphanediyl Tetrahydroindenylphenylphosphanediyl indenyl methylboranediyl methylindenylphenylboranediyl dimethylindenyl methylene trimethylindenyldimethylmethylene tetramethylindenyl diethylmethylene pentamethylindenyldibutylmethylene methylpropylindenyl dipropylmethylenedimethylpropylindenyl diphenylmethylene methyldipropylindenylditolylmethylene methylethylindenyl di(butylphenyl)methylenemethylbutylindenyl di(trimethylsilylphenyl)methylene ethylindenyldi(triethylsilylphenyl)methylene propylindenyl dibenzylmethylenebutylindenyl cyclotetramethylenemethylene pentylindenylcyclopentamethylenemethylene hexylindenyl ethylene heptylindenylmethylethylene octylindenyl dimethylethylene nonylindenyltrimethylethylene decylindenyl tetramethylethylene phenylindenylcyclopentylene (fluorophenyl)indenyl cyclohexylene (methylphenyl)indenylcycloheptylene biphenylindenyl cyclooctylene(bis(trifluoromethyl)phenyl)indenyl propanediyl napthylindenylmethylpropanediyl phenanthrylindenyl dimethylpropanediyl benzylindenyltrimethylpropanediyl benzindenyl tetramethylpropanediylcyclohexylindenyl pentamethylpropanediyl methylphenylindenylhexamethylpropanediyl ethylphenylindenyl tetramethyldisiloxylenepropylphenylindenyl vinylene methylnapthylindenyl ethene-1,1-diylethylnapthylindenyl divinylsilylene Propylnapthylindenyldipropenylsilylene (methylphenyl)indenyl dibutenylsilylene(dimethylphenyl)indenyl methylvinylsilylene (ethylphenyl)indenylmethylpropenylsilylene (diethylphenyl)indenyl methylbutenylsilylene(propylphenyl)indenyl dimethylsilylmethylene (dipropylphenyl)indenyldiphenylsilylmethylene methyltetrahydroindenyl dimethylsilylethyleneethyltetrahydroindenyl diphenylsilylethylene propyltetrahydroindenyldimethylsilylpropylene butyltetrahydroindenyl diphenylsilylpropylenephenyltetrahydroindenyl dimethylstannylene(diphenylmethyl)cyclopentadienyl diphenylstannylenedimethyltetrahydroindenyl trimethylsilylcyclopentadienyltriethylsilylcyclopentadienyl X₁ or X₂ trimethylgermylcyclopentadienylchloride trifluromethylcyclopentadienyl bromide cyclopenta[b]thienyliodide cyclopenta[b]furanyl fluoride cyclopenta[b]selenophenyl hydridecyclopenta[b]tellurophenyl methyl cyclopenta[b]pyrrolyl ethylcyclopenta[b]phospholyl propyl cyclopenta[b]arsolyl butylcyclopenta[b]stibolyl pentyl methylcyclopenta[b]thienyl hexylmethylcyclopenta[b]furanyl heptyl methylcyclopenta[b]selenophenyl octylmethylcyclopenta[b]tellurophenyl nonyl methylcyclopenta[b]pyrrolyl decylmethylcyclopenta[b]phosphoryl undecyl methylcyclopenta[b]arsolyl dodecylmethylcyclopenta[b]stibolyl tridecyl dimethylcyclopenta[b]thienyltetradecyl dimethylcyclopenta[b]furanyl pentadecyldimethylcyclopenta[b]pyrrolyl hexadecyl dimethylcyclopenta[b]phosphorylheptadecyl trimethylcyclopenta[b]thienyl octadecyltrimethylcyclopenta[b]furanyl nonadecyl trimethylcyclopenta[b]pyrrolyleicosyl trimethylcyclopenta[b]phosphoryl heneicosylethylcyclopenta[b]thienyl docosyl ethylcyclopenta[b]furanyl tricosylethylcyclopenta[b]pyrrolyl tetracosyl ethylcyclopenta[b]phosphorylpentacosyl diethylcyclopenta[b]thienyl hexacosyldiethylcyclopenta[b]furanyl heptacosyl diethylcyclopenta[b]pyrrolyloctacosyl diethylcyclopenta[b]phosphoryl nonacosyltriethylcyclopenta[b]thienyl triacontyl triethylcyclopenta[b]furanylphenyl triethylcyclopenta[b]pyrrolyl benzyltriethylcyclopenta[b]phosphoryl phenethyl propylcyclopenta[b]thienyltolyl propylcyclopenta[b]furanyl methoxy propylcyclopenta[b]pyrrolylethoxy propylcyclopenta[b]phosphoryl propoxydipropylcyclopenta[b]thienyl butoxy dipropylcyclopenta[b]furanyldimethylamido dipropylcyclopenta[b]pyrrolyl diethylamidodipropylcyclopenta[b]phosphory methylethylamidotripropylcyclopenta[b]thienyl phenoxy tripropylcyclopenta[b]furanylbenzoxy tripropylcyclopenta[b]pyrrolyl allyltripropylcyclopenta[b]phosphoryl butylcyclopenta[b]thienylbutylcyclopenta[b]furanyl X₁ and X₂ together butylcyclopenta[b]pyrrolylmethylidene butylcyclopenta[b]phosphoryl ethylidenedibutylcyclopenta[b]thienyl propylidene dibutylcyclopenta[b]furanyltetramethylene dibutylcyclopenta[b]pyrrolyl pentamethylenedibutylcyclopenta[b]phosphoryl- phospholyl hexamethylenetributylcyclopenta[b]thienyl ethylenedihydroxytributylcyclopenta[b]furanyl butadiene tributylcyclopenta[b]pyrrolylmethylbutadiene tributylcyclopenta[b]phospholyl phospholyldimethylbutadiene ethylmethylcyclopenta[b]thienyl pentadieneethylmethylcyclopenta[b]furanyl methylpentadieneethylmethylcyclopenta[b]pyrrolyl dimethylpentadieneethylmethylcyclopenta[b]phosphoryl hexadienemethylpropylcyclopenta[b]thienyl methylhexadienemethylpropylcyclopenta[b]furanyl dimethylhexadienemethylpropylcyclopenta[b]pyrrolyl methylpropylcyclopenta[b]phosphorylbutylmethylcyclopenta[b]thienyl M butylmethylcyclopenta[b]furanyltitanium butylmethylcyclopenta[b]pyrrolyl zirconiumbutylmethylcyclopenta[b]phosphoryl hafnium cyclopenta[c]thienylcyclopenta[c]furanyl cyclopenta[c]selenophenylcyclopenta[c]tellurophenyl cyclopenta[c]pyrrolyl cyclopenta[c]phosphorylcyclopenta[c]arsolyl cyclopenta[c]stibolyl methylcyclopenta[c]thienylmethylcyclopenta[c]furanyl methylcyclopenta[c]selenophenylmethylcyclopenta[c]tellurophenyl methylcyclopenta[c]pyrrolylmethylcyclopenta[c]phosphoryl methylcyclopenta[c]arsolylmethylcyclopenta[c]stibolyl dimethylcyclopenta[c]thienyldimethylcyclopenta[c]furanyl dimethylcyclopenta[c]pyrrolyldimethylcyclopenta[c]phosphoryl trimethylcyclopenta[c]thienyltrimethylcyclopenta[c]furanyl trimethylcyclopenta[c]pyrrolyltrimethylcyclopenta[c]phosphoryl ethylcyclopenta[c]thienylethylcyclopenta[c]furanyl ethylcyclopenta[c]pyrrolylethylcyclopenta[c]phosphoryl diethylcyclopenta[c]thienyldiethylcyclopenta[c]furanyl diethylcyclopenta[c]pyrrolyldiethylcyclopenta[c]phosphoryl triethylcyclopenta[c]thienyltriethylcyclopenta[c]furanyl triethylcyclopenta[c]pyrrolyltriethylcyclopenta[c]phosphoryl propylcyclopenta[c]thienylpropylcyclopenta[c]furanyl propylcyclopenta[c]pyrrolylpropylcyclopenta[c]phosphoryl dipropylcyclopenta[c]thienyldipropylcyclopenta[c]furanyl dipropylcyclopenta[c]pyrrolyldipropylcyclopenta[c]phosphoryl tripropylcyclopenta[c]thienyltripropylcyclopenta[c]furanyl tripropylcyclopenta[c]pyrrolyltripropylcyclopenta[c]phosphoryl- phosphorylphospholylbutylcyclopenta[c]thienyl butylcyclopenta[c]furanylbutylcyclopenta[c]pyrrolyl butylcyclopenta[c]phosphoryldibutylcyclopenta[c]thienyl dibutylcyclopenta[c]furanyldibutylcyclopenta[c]pyrrolyl dibutylcyclopenta[c]phosphoryltributylcyclopenta[c]thienyl tributylcyclopenta[c]furanyltributylcyclopenta[c]pyrrolyl tributylcyclopenta[c]phosphorylethylmethylcyclopenta[c]thienyl ethylmethylcyclopenta[c]furanylethylmethylcyclopenta[c]pyrrolyl ethylmethylcyclopenta[c]phosphorylmethylpropylcyclopenta[c]thienyl methylpropylcyclopenta[c]furanylmethylpropylcyclopenta[c]pyrrolyl methylpropylcyclopenta[c]phosphorylbutylmethylcyclopenta[c]thienyl butylmethylcyclopenta[c]furanylbutylmethylcyclopenta[c]pyrrolyl butylmethylcyclopenta[c]phosphoryl

In a preferred embodiment of the invention, Cp is the same as Cp* and isa substituted or unsubstituted cyclopentadienyl, indenyl ortetrahydroindenyl ligand or fluorenyl. In another preferred embodimentof the invention, Cp is different from Cp* and is a substituted orunsubstituted cyclopentadienyl, indenyl or tetrahydroindenyl ligand orfluorenyl.

Preferred metallocene compounds (pre-catalysts) which, according to thepresent invention, provide catalyst systems, which are specific to theproduction of poly-α-olefins having high catalyst productivity andconvert C₃ to C₃₀ alpha-olefins with comparable reactivities. Thesecompounds can have any one of the symmetry groups classified as C₂,pseudo-C₂, C_(2v), or C_(s) symmetry, and include the racemic and mesoversions of: bis(indenyl)zirconium dichloride, bis(indenyl)zirconiumdimethyl, bis(methylindenyl)zirconium dichloride,bis(methylindenyl)zirconium dimethyl, bis(dimethylindenyl)zirconiumdichloride, bis(dimethylindenyl)zirconium dimethyl,bis(alkyllindenyl)zirconium dichloride, bis(alkylindenyl)zirconiumdimethyl, bis(dialkylindenyl)zirconium dichloride,bis(dialkylindenyl)zirconium dimethyl, dimethylsilylbis(indenyl)zirconium dichloride, dimethylsilylbis(indenyl) zirconium dimethyl,diphenylsilylbis(indenyl) zirconium dichloride,diphenylsilylbis(indenyl) zirconium dimethyl,methylphenylsilylbis(indenyl) zirconium dichloride,methylphenylsilylbis(indenyl) zirconium dimethyl, ethylenebis(indenyl)zirconium dichloride, ethylenebis(indenyl) zirconium dimethyl,methylenebis(indenyl) zirconium dichloride, methylenebis(indenyl)zirconium dimethyl, dimethylsilylbis(indenyl) hafnium dichloride,dimethylsilylbis(indenyl) hafnium dimethyl, diphenylsilylbis(indenyl)hafnium dichloride, diphenylsilylbis(indenyl) hafnium dimethyl,methylphenylsilylbis(indenyl) hafnium dichloride,methylphenylsilylbis(indenyl) hafnium dimethyl, ethylenebis(indenyl)hafnium dichloride, ethylenebis(indenyl) hafnium dimethyl,methylenebis(indenyl) hafnium dichloride, methylenebis(indenyl) hafniumdimethyl, dimethylsilylbis(tetrahydroindenyl) zirconium dichloride,dimethylsilylbis(tetrahydroindenyl) zirconium dimethyl,diphenylsilylbis(tetrahydroindenyl) zirconium dichloride,diphenylsilylbis(tetrahydroindenyl) zirconium dimethyl,methylphenylsilylbis(tetrahydroindenyl) zirconium dichloride,methylphenylsilylbis(tetrahydroindenyl) zirconium dimethyl,ethylenebis(tetrahydroindenyl) zirconium dichloride,ethylenebis(tetrahydroindenyl) zirconium dimethyl,methylenebis(tetrahydroindenyl) zirconium dichloride,methylenebis(tetrahydroindenyl) zirconium dimethyl,dimethylsilylbis(tetrahydroindenyl) hafnium dichloride,dimethylsilylbis(tetrahydroindenyl) hafnium dimethyl,diphenylsilylbis(tetrahydroindenyl) hafnium dichloride,diphenylsilylbis(tetrahydroindenyl) hafnium dimethyl,methylphenylsilylbis(tetrahydroindenyl) hafnium dichloride,methylphenylsilylbis(tetrahydroindenyl) hafnium dimethyl,ethylenebis(tetrahydroindenyl) hafnium dichloride,ethylenebis(tetrahydroindenyl) hafnium dimethyl,methylenebis(tetrahydroindenyl) hafnium dichloride,methylenebis(tetrahydroindenyl) hafnium dimethyl, dimethylsilylbis(4,7-dimethylindenyl) zirconium dichloride,dimethylsilylbis(4,7-dimethylindenyl) zirconium dimethyl,diphenylsilylbis(4,7-dimethylindenyl) zirconium dichloride,diphenylsilylbis(4,7-dimethylindenyl) zirconium dimethyl,methylphenylsilylbis(4,7-dimethylindenyl) zirconium dichloride,methylphenylsilylbis(4,7-dimethylindenyl) zirconium dimethyl,ethylenebis(4,7-dimethylindenyl) zirconium dichloride,ethylenebis(4,7-dimethylindenyl) zirconium dimethyl,methylenebis(4,7-dimethylindenyl) zirconium dichloride,methylenebis(4,7-dimethylindenyl) zirconium dimethyl,dimethylsilylbis(4,7-dimethylindenyl) hafnium dichloride,dimethylsilylbis(4,7-dimethylindenyl) hafnium dimethyl,diphenylsilylbis(4,7-dimethylindenyl) hafnium dichloride,diphenylsilylbis(4,7-dimethylindenyl) hafnium dimethyl,methylphenylsilylbis(4,7-dimethylindenyl) hafnium dichloride,methylphenylsilylbis(4,7-dimethylindenyl) hafnium dimethyl,ethylenebis(4,7-dimethylindenyl) hafnium dichloride,ethylenebis(4,7-dimethylindenyl) hafnium dimethyl,methylenebis(4,7-dimethylindenyl) hafnium dichloride,methylenebis(4,7-dimethylindenyl) hafnium dimethyl,dimethylsilylbis(2-methyl-4-napthylindenyl) zirconium dichloride,dimethylsilylbis(2-methyl-4-napthylindenyl) zirconium dimethyl,diphenylsilylbis(2-methyl-4-napthylindenyl) zirconium dichloride,dimethylsilylbis(2, 3-dimethylcyclopentadienyl) zirconium dichloride,dimethylsilylbis(2,3-dimethyl cyclopentadienyl) zirconium dimethyl,diphenylsilylbis(2,3-dimethylcyclopentadienyl) zirconium dichloride,diphenylsilylbis(2,3-dimethylcyclopentadienyl) zirconium dimethyl,methylphenylsilylbis(2,3-dimethylcyclopentadienyl) zirconium dichloride,methylphenylsilylbis(2,3-dimethylcyclopentadienyl) zirconium dimethyl,ethylenebis(2,3-dimethylcyclopentadienyl) zirconium dichloride,ethylenebis(2,3-dimethylcyclopentadienyl) zirconium dimethyl,methylenebis(2,3-dimethylcyclopentadienyl) zirconium dichloride,methylenebis(2,3-dimethylcyclopentadienyl) zirconium dimethyl,dimethylsilylbis(2,3-dimethylcyclopentadienyl) hafnium dichloride,dimethylsilylbis(2,3 dimethylcyclopentadienyl) hafnium dimethyl,diphenylsilylbis(2,3-dimethylcyclopentadienyl) hafnium dichloride,diphenylsilylbis(2,3-dimethylcyclopentadienyl) hafnium dimethyl,methylphenylsilylbis(2,3-dimethylcyclopentadienyl) hafnium dichloride,methylphenylsilylbis(2, 3-dimethylcyclopentadienyl) hafnium dimethyl,ethylenebis(2,3-dimethylcyclopentadienyl) hafnium dichloride,ethylenebis(2,3-dimethylcyclopentadienyl) hafnium dimethyl,methylenebis(2,3-dimethylcyclopentadienyl) hafnium dichloride,methylenebis(2, 3-dimethylcyclopentadienyl) hafnium dimethyl,dimethylsilylbis(3-trimethylsilylcyclopentadienyl) zirconium dichloride,dimethylsilylbis(3-trimethylsilylcyclopentadienyl) zirconium dimethyl,diphenylsilylbis(3-trimethylsilylcyclopentadienyl) zirconium dichloride,diphenylsilylbis(3-trimethylsilylcyclopentadienyl) zirconium dimethyl,methylphenylsilylbis(3-trimethylsilylcyclopentadienyl) zirconiumdichloride, methylphenylsilylbis(3-trimethylsilylcyclopentadienyl)zirconium dimethyl, ethylenebis(3-trimethylsilylcyclopentadienyl)zirconium dichloride, ethylenebis(3-trimethylsilylcyclopentadienyl)zirconium dimethyl, methylenebis(3-trimethylsilylcyclopentadienyl)zirconium dichloride, methylenebis(3-trimethylsilylcyclopentadienyl)zirconium dimethyl, dimethylsilylbis(3-trimethylsilylcyclopentadienyl)hafnium dichloride, dimethylsilylbis(3-trimethylsilylcyclopentadienyl)hafnium dimethyl, diphenylsilylbis(3-trimethylsilylcyclopentadienyl)hafnium dichloride, diphenylsilylbis(3-trimethylsilylcyclopentadienyl)hafnium dimethyl, methylphenylsilylbis(3-trimethylsilylcyclopentadienyl)hafnium dichloride,methylphenylsilylbis(3-trimethylsilylcyclopentadienyl) hafnium dimethyl,ethylenebis(3-trimethylsilylcyclopentadienyl) hafnium dichloride,ethylenebis(3-trimethylsilylcyclopentadienyl) hafnium dimethyl,methylenebis(3-trimethylsilylcyclopentadienyl) hafnium dichloride, andmethylenebis(3-trimethylsilylcyclopentadienyl) hafnium dimethyl. Anotherset of preferred metallocene catalysts include substituted unbridgedbis(R₁,R₂,R₃,R₄,R₅-cyclopentadienyl) zirconium dichlorides or dimethylswhere the R₁ to R₅ groups can be same or different and can beindependently chosen from H, C₁ to C₂₀ hydrocarbyl radicals. Thesemetallocenes when activated with MAO or NCA co-catalysts and optionallywith co-activators have high catalyst productivity and more importantlyhave comparable reactivity for all alpha-olefins with C₃ to C₃₀ range.Specific examples are bis(alkylcyclopentadienyl) zirconium dichlorides(alkyl=C₁ to C₂₀-alkyl group, specially, methyl, ethyl, n-propyl,n-butyl, n-pentyl, n-hexyl, etc. and iso-propyl, isobutyl, t-butylgroups, etc.), bis(1,2-dimethylcyclopentadienyl) zirconium dichloride,bis(1,3-dimethylcyclopentadienyl) zirconium dichloride,bis(1-methyl-3-n-propyl cyclopentadienyl) zirconium dichloride,bis(1-methyl-3-ethylcyclopentadienyl) zirconium dichloride,bis(1-methyl-3-n-propyl cyclopentadienyl) zirconium dichloride,bis(1-methyl-2-n-butyl cyclopentadienyl) zirconium dichloride,bis(1-methyl-2-n-propyl cyclopentadienyl) zirconium dichloride,bis(1-methyl-2-ethylcyclopentadienyl) zirconium dichloride,bis(1,2,3-trimethyl cyclopentadienyl) zirconium dichloride,bis(1,2,4-trimethylcyclopentadienyl) zirconium di chloride,bis(1,2-dimethyl-4-ethylcyclopentadienyl) zirconium dichloride,bis(1,2-dimethyl-4-n-propylcyclopentadienyl) zirconium dichloride,bis(1,2-dimethyl-4-n-butyl cyclopentadienyl) zirconium dichloride,bis(tetramethylcyclopentadienyl) zirconium dichloride,bis(pentamethylcyclopentadienyl) zirconium dichloride, etc.

Particularly preferred species are the racemic and meso versions of:dimethylsilylbis(indenyl) zirconium dichloride,dimethylsilylbis(indenyl) zirconium dimethyl, ethylenebis(indenyl)zirconium dichloride, ethylenebis(indenyl) zirconium dimethyl,dimethylsilylbis(tetrahydorindenyl) zirconium dichloride,dimethylsilylbis(tetrahydorindenyl) zirconium dimethyl,ethylenebis(tetrahydorindenyl) zirconium dichloride,ethylenebis(tetrahydorindenyl) zirconium dimethyl,dimethylsilylbis(4,7-dimethylindenyl) zirconium dichloride,dimethylsilylbis(4,7-dimethylindenyl) zirconium dimethyl,ethylenebis(4,7-dimethylindenyl) zirconium dichloride,ethylenebis(4,7-dimethylindenyl) zirconium dimethyl,dimethylsilylbis(indenyl) hafnium dichloride, dimethylsilylbis(indenyl)hafnium dimethyl, ethylenebis(indenyl) hafnium dichloride,ethylenebis(indenyl) hafnium dimethyl,dimethylsilylbis(tetrahydorindenyl) hafnium dichloride,dimethylsilylbis(tetrahydorindenyl) hafnium dimethyl,ethylenebis(tetrahydorindenyl) hafnium dichloride,ethylenebis(tetrahydorindenyl) hafnium dimethyl,dimethylsilylbis(4,7-dimethylindenyl) hafnium dichloride,dimethylsilylbis(4,7-dimethylindenyl) hafnium dimethyl,ethylenebis(4,7-dimethylindenyl) hafnium dichloride, andethylenebis(4,7-dimethylindenyl) hafnium dimethyl. Other preferredcatalysts includediphenylmethylidene(cyclopentadienyl)(9-fluorenyl)zirconium dichloride,iso-propylidene(cyclopentadienyl)(9-fluorenyl)zirconium dichloride,iso-propylidene(3-methylcyclopentadienyl)(9-fluorenyl)zirconiumdichloride, ethylenebis(9-fluorenyl)zirconium dichloride,dimethylsilylbis(9-fluorenyl)zirconium dichloride, dimethylsilyl(cyclopentadienyl)(9-fluorenyl)zirconium dichloride, diphenylsilyl(cyclopentadienyl)(9-fluorenyl)zirconium dichloride, their analogsof dimethyls or the analogs of hafnium metallocenes.

The metallocene compounds, when activated by a per se commonly knownactivator such as methyl aluminoxane, form active catalysts for thepolymerization or oligomerization of olefins. Activators that may beused include aluminoxanes such as methyl aluminoxane (or MAO, shown inFormula II, above), modified methyl aluminoxane, ethyl aluminoxane,iso-butyl aluminoxane and the like, Lewis acid activators includingtriphenyl boron, tris-perfluorophenyl boron, tris-perfluorophenylaluminum and the like, ionic activators including dimethylaniliniumtetrakis perfluorophenyl borate, triphenyl carbonium tetrakisperfluorophenyl borate, dimethylanilinium tetrakis perfluorophenylaluminate, and the like, and non-coordinating anions such as shown inFormula III.

A co-activator is a compound capable of alkylating the transition metalcomplex, such that when used in combination with an activator, an activecatalyst is formed. Co-activators include aluminoxanes such as methylaluminoxane, modified aluminoxanes such as modified methyl aluminoxane,and aluminum alkyls such trimethyl aluminum, tri-isobutyl aluminum,triethyl aluminum, and tri-isopropyl aluminum, tri-n-hexyl aluminum,tri-n-octyl aluminum, tri-n-decyl aluminum or tri-n-dodecyl aluminum.Co-activators are typically used in combination with Lewis acidactivators and ionic activators when the pre-catalyst is not adihydrocarbyl or dihydride complex. Sometimes co-activators are alsoused as scavengers to deactivate impurities in feed or reactors.

The aluminoxane component useful as an activator typically is preferablyan oligomeric aluminum compound represented by the general formula(R^(x)—Al—O)_(n), which is a cyclic compound, or R^(x)(R^(x)—Al—O)_(n)AlR^(x) ₂, which is a linear compound. The most commonaluminoxane is a mixture of the cyclic and linear compounds. In thegeneral aluminoxane formula, R^(x) is independently a C₁-C₂₀ alkylradical, for example, methyl, ethyl, propyl, butyl, pentyl, isomersthereof, and the like, and “n” is an integer from 1-50. Most preferably,R^(x) is methyl and “n” is at least 4. Methyl aluminoxane and modifiedmethyl aluminoxanes are most preferred. For further descriptions see, EP0 279 586, EP 0 594 218, EP 0 561 476, WO94/10180 and U.S. Pat. Nos.4,665,208, 4,874,734, 4,908,463, 4,924,018, 4,952,540, 4,968,827,5,041,584, 5,091,352, 5,103,031, 5,157,137, 5,204,419, 5,206,199,5,235,081, 5,248,801, 5,329,032, 5,391,793, and 5,416,229.

When an aluminoxane or modified aluminoxane is used, thecatalyst-precursor-to-activator molar ratio (based on the metals, e.g.,Zr or Hf to Al) is from about 1:3000 to 10:1; alternatively, 1:2000 to10:1; alternatively 1:1000 to 10:1; alternatively, 1:500 to 1:1;alternatively 1:300 to 1:1; alternatively 1:250 to 1:1, alternatively1:200 to 1:1; alternatively 1:100 to 1:1; alternatively 1:50 to 1:1;alternatively 1:10 to 1:1. When the activator is an aluminoxane(modified or unmodified), some embodiments select the maximum amount ofactivator at a 5000-fold molar excess over the catalyst precursor (permetal catalytic site). The preferred minimumactivator-to-catalyst-precursor ratio is 1:1 molar ratio.

Ionic activators (which in embodiments may be used in combination with aco-activator) may be used in the practice of this invention. Ionicactivators, sometimes referred to as non-coordinating anion (NCA)activators, usually refer to those activators that have distinctiveionic character in their active states, even though these activators areneutral chemical compounds. They are exemplified by Formula 2, above,which a preferred ionic activator; Preferably, discrete ionic activatorssuch as [Me₂PhNH][B(C₆F₅)₄], [R₃NH][B(C₆F₅)₄], [R₂NH₂][B(C₆F₅)₄],[RNH₃][B(C₆F₅)₄], [R₄N][B(C₆F₅)₄], [Ph₃C][B(C₆F₅)₄],[Me₂PhNH][B((C₆H₃-3,5-(CF₃)₂))₄], [Ph₃C][B((C₆H₃-3,5-(CF₃)₂))⁴],[NH₄][B(C₆H₅)₄] or Lewis acidic activators such as B(C₆F₅)₃ or B(C₆H₅)₃can be used, where Ph is phenyl and Me is methyl, R═C₁ to C₁₆ alkylgroups. Preferred co-activators, when used, are aluminoxanes such asmethyl aluminoxane, modified aluminoxanes such as modified methylaluminoxane, and aluminum alkyls such as tri-isobutyl aluminum, andtrimethyl aluminum, triethyl aluminum, and tri-isopropyl aluminum,tri-n-hexyl aluminum, tri-n-octyl aluminum, tri-n-decyl aluminum ortri-n-dodecyl aluminum. The preferred ionic activators are N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, tetra-methyl aniliniumtetrakis(pentafluorophenyl)borate, tetradecylaniliniumtetrakis(pentafluorophenyl)borate, tetrahexadecylaniliniumtetrakis(pentafluorophenyl)borate, [Ph₃C][B(C₆F₅)₄], B(C₆F₅)₃.

It is within the scope of this invention to use an ionizing orstoichiometric activator, neutral or ionic, such as tri(n-butyl)ammonium tetrakis(pentafluorophenyl) borate, a tris(perfluorophenyl)boron metalloid precursor or a tris(perfluoronaphthyl) boron metalloidprecursor, polyhalogenated heteroborane anions (e.g., WO 98/43983),boric acid (e.g., U.S. Pat. No. 5,942,459) or combination thereof.

Examples of neutral stoichiometric activators include tri-substitutedboron, tellurium, aluminum, gallium and indium or mixtures thereof. Thethree substituent groups are each independently selected from alkyls,alkenyls, halogen, substituted alkyls, aryls, arylhalides, alkoxy andhalides. Preferably, the three groups are independently selected fromhalogen, mono- or multicyclic (including halosubstituted) aryls, alkyls,and alkenyl compounds and mixtures thereof, preferred are alkenyl groupshaving 1 to 20 carbon atoms, alkyl groups having 1 to 20 carbon atoms,alkoxy groups having 1 to 20 carbon atoms and aryl groups having 3 to 20carbon atoms (including substituted aryls). More preferably, the threegroups are alkyls having 1 to 4 carbon groups, phenyl, naphthyl ormixtures thereof. Even more preferably, the three groups arehalogenated, preferably fluorinated, aryl groups. Most preferably, theneutral stoichiometric activator is tris(perfluorophenyl) boron ortris(perfluoronaphthyl) boron.

Ionic stoichiometric activator compounds may contain an active proton,or some other cation associated with, but not coordinated to, or onlyloosely coordinated to, the remaining ion of the ionizing compound. Suchcompounds and the like are described in European publications EP-A-0 570982, EP-A-0 520 732, EP-A-0 495 375, EP-B1-0 500 944, EP-A-0 277 003 andEP-A-0 277 004, and U.S. Pat. Nos. 5,153,157, 5,198,401, 5,066,741,5,206,197, 5,241,025, 5,384,299 and 5,502,124 and U.S. patentapplication Ser. No. 08/285,380, filed Aug. 3, 1994.

Ionic catalysts can be prepared by reacting a transition metal compoundwith an activator, such as B(C₆F₆)₃, which upon reaction with thehydrolyzable ligand (X′) of the transition metal compound forms ananion, such as ([B(C₆F₅)₃(X′)]⁻), which stabilizes the cationictransition metal species generated by the reaction. The catalysts canbe, and preferably are, prepared with activator components which areionic compounds or compositions. However preparation of activatorsutilizing neutral compounds is also contemplated by this invention.

Compounds useful as an activator component in the preparation of theionic catalyst systems used in the process of this invention comprise acation, which is preferably a Brønsted acid capable of donating aproton, and a compatible non-coordinating anion which anion isrelatively large (bulky), capable of stabilizing the active catalystspecies which is formed when the two compounds are combined and saidanion will be sufficiently labile to be displaced by olefinic,diolefinic, and acetylenically unsaturated substrates or other neutralLewis bases such as ethers, nitriles and the like. Two classes ofcompatible non-coordinating anions have been disclosed in EP-277,003 andEP 277,004 published 1988: 1) anionic coordination complexes comprisinga plurality of lipophilic radicals covalently coordinated to, andshielding, a central charge-bearing metal or metalloid core, and 2)anions comprising a plurality of boron atoms such as carboranes,metallacarboranes and boranes.

In a preferred embodiment, the stoichiometric activators include acation and an anion component, and may be represented by the followingformula:

(L**-H)_(d) ⁺(A^(d−))

wherein L** is an neutral Lewis base;H is hydrogen;(L**-H)⁺ is a Brønsted acidA^(d−) is a non-coordinating anion having the charge d−d is an integer from 1 to 3.

The cation component, (L**-H)_(d) ⁺ may include Brønsted acids such asprotons or protonated Lewis bases or reducible Lewis acids capable ofprotonating or abstracting a moiety, such as an alkyl or aryl, from theprecatalyst after alkylation. The activating cation (L**-H)_(d) ⁺ may bea Brønsted acid, capable of donating a proton to the alkylatedtransition metal catalytic precursor resulting in a transition metalcation, including ammoniums, oxoniums, phosphoniums, silyliums, andmixtures thereof, preferably ammoniums of methylamine, aniline,dimethylamine, diethylamine, N-methylaniline, diphenylamine,trimethylamine, triethylamine, N,N-dimethylaniline, methyldiphenylamine,pyridine, p-bromo N,N-dimethylaniline, p-nitro-N,N-dimethylaniline,phosphoniums from triethylphosphine, triphenylphosphine, anddiphenylphosphine, oxomiuns from ethers such as dimethyl ether, diethylether, tetrahydrofuran and dioxane, sulfoniums from thioethers, such asdiethyl thioethers and tetrahydrothiophene, and mixtures thereof. Theactivating cation (L**-H)_(d) ⁺ may also be a moiety such as silver,tropylium, carbeniums, ferroceniums and mixtures, preferably carboniumsand ferroceniums; most preferably triphenyl carbonium.

The anion component A^(d−) include those having the formula[M^(k+)Q_(n)]^(d−) wherein k is an integer from 1 to 3; n is an integerfrom 2-6; n−k=d; M is an element selected from Group 13 of the PeriodicTable of the Elements, preferably boron or aluminum, and Q isindependently a hydride, bridged or unbridged dialkylamido, halide,alkoxide, aryloxide, hydrocarbyl, substituted hydrocarbyl, halocarbyl,substituted halocarbyl, and halosubstituted-hydrocarbyl radicals, said Qhaving up to 20 carbon atoms with the proviso that in not more than oneoccurrence is Q a halide. Preferably, each Q is a fluorinatedhydrocarbyl group having 1 to 20 carbon atoms, more preferably each Q isa fluorinated aryl group, and most preferably each Q is a pentafluorylaryl group. Examples of suitable A^(d−) also include diboron compoundsas disclosed in U.S. Pat. No. 5,447,895, which is fully incorporatedherein by reference.

Illustrative, but not limiting examples of boron compounds which may beused as an activating cocatalyst in combination with a co-activator inthe preparation of the improved catalysts of this invention aretri-substituted ammonium salts such as: trimethylammoniumtetraphenylborate, triethylammonium tetraphenylborate, tripropylammoniumtetraphenylborate, tri(n-butyl)ammonium tetraphenylborate,tri(tert-butyl)ammonium tetraphenylborate, N,N-dimethylaniliniumtetraphenylborate, N,N-diethylanilinium tetraphenylborate,N,N-dimethyl-(2,4,6-trimethylanilinium) tetraphenylborate,trimethylammonium tetrakis(pentafluorophenyl)borate, triethylammoniumtetrakis(pentafluorophenyl)borate, tripropylammoniumtetrakis(pentafluorophenyl)borate, tri(n-butyl)ammoniumtetrakis(pentafluorophenyl)borate, tri(sec-butyl)ammoniumtetrakis(pentafluorophenyl)borate, N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, N,N-diethylaniliniumtetrakis(pentafluorophenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(pentafluorophenyl)borate, trimethylammoniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, triethylammoniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, tripropylammoniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, tri(n-butyl)ammoniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, dimethyl(tert-butyl)ammoniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, N,N-dimethylaniliniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, N,N-diethylaniliniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis-(2,3,4,6-tetrafluorophenyl)borate, trimethylammoniumtetrakis(perfluoronaphthyl)borate, triethylammoniumtetrakis(perfluoronaphthyl)borate, tripropylammoniumtetrakis(perfluoronaphthyl)borate, tri(n-butyl)ammoniumtetrakis(perfluoronaphthyl)borate, tri(tert-butyl)ammoniumtetrakis(perfluoronaphthyl)borate, N,N-dimethylaniliniumtetrakis(perfluoronaphthyl)borate, N,N-diethylaniliniumtetrakis(perfluoronaphthyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(perfluoronaphthyl)borate, trimethylammoniumtetrakis(perfluorobiphenyl)borate, triethylammoniumtetrakis(perfluorobiphenyl)borate, tripropylammoniumtetrakis(perfluorobiphenyl)borate, tri(n-butyl)ammoniumtetrakis(perfluorobiphenyl)borate, tri(tert-butyl)ammoniumtetrakis(perfluorobiphenyl)borate, N,N-dimethylaniliniumtetrakis(perfluorobiphenyl)borate, N,N-diethylaniliniumtetrakis(perfluorobiphenyl)borate, N,N-dimethyl-(2,4,6-trimethylanilinium) tetrakis(perfluorobiphenyl)borate,trimethylammonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,triethylammonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,tripropylammonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,tri(n-butyl)ammonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,tri(tert-butyl)ammonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,N,N-dimethylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,N,N-diethylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, and dialkyl ammoniumsalts such as: di-(iso-propyl)ammoniumtetrakis(pentafluorophenyl)borate, and dicyclohexylammoniumtetrakis(pentafluorophenyl)borate; and other salts such astri(o-tolyl)phosphonium tetrakis(pentafluorophenyl)borate,tri(2,6-dimethylphenyl)phosphonium tetrakis(pentafluorophenyl)borate,tropylium tetraphenylborate, triphenylcarbenium tetraphenylborate,triphenylphosphonium tetraphenylborate, tri ethyl silyliumtetraphenylborate, benzene(diazonium)tetraphenylborate, tropyliumtetrakis(pentafluorophenyl)borate, triphenylcarbeniumtetrakis(pentafluorophenyl)borate, triphenylphosphoniumtetrakis(pentafluorophenyl)borate, triethylsilyliumtetrakis(pentafluorophenyl)borate, benzene(diazonium)tetrakis(pentafluorophenyl)borate, tropylium tetrakis-(2,3,4,6-tetrafluorophenyl)borate, triphenylcarbeniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, triphenylphosphoniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, tri ethyl silyliumtetrakis-(2,3,4, 6-tetrafluorophenyl)borate, benzene(diazonium)tetrakis-(2,3,4,6-tetrafluorophenyl)borate, tropyliumtetrakis(perfluoronaphthyl)borate, triphenylcarbeniumtetrakis(perfluoronaphthyl)borate, triphenylphosphoniumtetrakis(perfluoronaphthyl)borate, tri ethyl silyliumtetrakis(perfluoronaphthyl)borate, benzene(diazonium)tetrakis(perfluoronaphthyl)borate, tropyliumtetrakis(perfluorobiphenyl)borate, triphenylcarbeniumtetrakis(perfluorobiphenyl)borate, triphenylphosphoniumtetrakis(perfluorobiphenyl)borate, tri ethyl silyliumtetrakis(perfluorobiphenyl)borate, benzene(diazonium)tetrakis(perfluorobiphenyl)borate, tropyliumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbeniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylphosphoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triethyl silyliumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, and benzene(diazonium)tetrakis(3,5-bis(trifluoromethyl)phenyl)borate.

Most preferably, the ionic stoichiometric activator (L**-H)_(d)⁺(A^(d−)) is N,N-dimethylanilinium tetrakis(perfluorophenyl)borate,N,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate,N,N-dimethylanilinium tetrakis(perfluorobiphenyl)borate,N,N-dimethylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,triphenylcarbenium tetrakis(perfluoronaphthyl)borate, triphenylcarbeniumtetrakis(perfluorobiphenyl)borate, triphenylcarbeniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, or triphenylcarbeniumtetra(perfluorophenyl)borate.

The catalyst precursors can also be activated with cocatalysts oractivators that comprise non-coordinating anions containingmetalloid-free cyclopentadienide ions. These are described in U.S.Patent Publication 2002/0058765 A1, published on 16 May 2002, and forthe instant invention, require the addition of a co-activator to thecatalyst pre-cursor.

“Compatible” non-coordinating anions are those which are not degraded toneutrality when the initially formed complex decomposes. Further, theanion will not transfer an anionic substituent or fragment to the cationso as to cause it to form a neutral transition metal compound and aneutral by-product from the anion. Preferred non-coordinating anionsuseful in accordance with this invention are those that are compatible,stabilize the transition metal complex cation in the sense of balancingits ionic charge at +1, yet retain sufficient lability to permitdisplacement by an ethylenically or acetylenically unsaturated monomerduring polymerization. These types of cocatalysts are sometimes usedwith scavengers. They have the general compositions of R₁, R₂, R₃—Alwhere R₁, R₂ and R₃ can be H or any of C₁ to C₂₀ hydrocarbyl radicals.Examples of the trialkylaluminum compounds include but are not limitedto tri-iso-butyl aluminum, tri-n-octyl aluminum, tri-n-hexyl aluminum,triethylaluminum or trimethylaluminum, tri-n-decyl aluminum,tri-n-dodecyl aluminum.

Invention processes also can employ cocatalyst compounds or activatorcompounds that are initially neutral Lewis acids but form a cationicmetal complex and a noncoordinating anion, or a zwitterionic complexupon reaction with the alkylated transition metal compounds. Thealkylated metallocene compound is formed from the reaction of thecatalyst pre-cursor and the co-activator. For example,tris(pentafluorophenyl) boron or aluminum act to abstract a hydrocarbylligand to yield an invention cationic transition metal complex andstabilizing noncoordinating anion, see EP-A-0 427 697 and EP-A-0 520 732for illustrations of analogous Group-4 metallocene compounds. Also, seethe methods and compounds of EP-A-0 495 375. For formation ofzwitterionic complexes using analogous Group 4 compounds, see U.S. Pat.Nos. 5,624,878; 5,486,632; and 5,527,929.

Additional neutral Lewis acids are known in the art and are suitable forabstracting formal anionic ligands. See in particular the review articleby E. Y.-X. Chen and T. J. Marks, “Cocatalysts for Metal-CatalyzedOlefin Polymerization: Activators, Activation Processes, andStructure-Activity Relationships”, Chem. Rev., 100, 1391-1434 (2000).

When the cations of noncoordinating anion precursors are Brønsted acidssuch as protons or protonated Lewis bases (excluding water), orreducible Lewis acids such as ferrocenium or silver cations, or alkalior alkaline earth metal cations such as those of sodium, magnesium orlithium, the catalyst-precursor-to-activator molar ratio may be anyratio. Combinations of the described activator compounds may also beused for activation.

When an ionic or neutral stoichiometric NCA-type activator is used, thecatalyst-precursor-to-activator molar ratio is from 1:10 to 1:1; 1:10 to10:1; 1:10 to 2:1; 1:10 to 3:1; 1:10 to 5:1; 1:2 to 1.2:1; 1:2 to 10:1;1:2 to 2:1; 1:2 to 3:1; 1:2 to 5:1; 1:3 to 1.2:1; 1:3 to 10:1; 1:3 to2:1; 1:3 to 3:1; 1:3 to 5:1; 1:5 to 1:1; 1:5 to 10:1; 1:5 to 2:1; 1:5 to3:1; 1:5 to 5:1; 1:1 to 1:1.2. The catalyst-precursor-to-co-activatormolar ratio is from 1:500 to 1:1, 1:100 to 100:1; 1:75 to 75:1; 1:50 to50:1; 1:25 to 25:1; 1:15 to 15:1; 1:10 to 10:1; 1:5 to 5:1, 1:2 to 2:1;1:100 to 1:1; 1:75 to 1:1; 1:50 to 1:1; 1:25 to 1:1; 1:15 to 1:1; 1:10to 1:1; 1:5 to 1:1; 1:2 to 1:1; 1:10 to 2:1.

Preferred activators and activator/co-activator combinations includemethylaluminoxane, modified methylaluminoxane, mixtures ofmethylaluminoxane with dimethylaniliniumtetrakis(pentafluorophenyl)borate or tris(pentafluorophenyl)boron, andmixtures of trialkyl aluminum, preferable any one of tri-isobutylaluminum, triethyl aluminum, tri-n-alkyl aluminum or trimethyl aluminumor their combination, with dimethylaniliniumtetrakis(pentafluorophenyl)borate or tris(pentafluorophenyl)boron ortheir analogs.

In some embodiments, scavenging compounds are used with stoichiometricactivators. Typical aluminum or boron alkyl components useful asscavengers are represented by the general formula R^(x)JZ₂ where J isaluminum or boron, R^(x) is as previously defined above, and each Z isindependently R^(x) or a different univalent anionic ligand such ashalogen (Cl, Br, I), alkoxide (OR′) and the like. R^(x) is a H or anyradical chosen from the C₁ to C₂₀ hydrocarbyl radicals. Most preferredaluminum alkyls include triethylaluminum, diethylaluminum chloride,tri-iso-butylaluminum, tri-n-octylaluminum. tri-n-hexylaluminum,trimethylaluminum and the like. Preferred boron alkyls includetriethylboron. Scavenging compounds may also be aluminoxanes andmodified aluminoxanes including methylaluminoxane and modifiedmethylaluminoxane. The scavenger can be the same or different from theco-activator used for the catalyst system.

An active catalyst solution can be prepared by dissolving metallocene,activator including methylaluminoxane or NCA, co-activator and/orscavenger in proper pre-purified solvent individually. Then combine allthe component solutions in any one of the following orders to giveactive catalyst solution. Method (a)—add metallocene solution toco-activator and/or scavenger solution, followed by addition ofactivator. Method (b)—combine metallocene solution with activatorsolution and add this mixture into co-activator and/or scavengersolution. Method (c)—add activator solution to co-activator and/orscavenger solution, followed by metallocene solution. Sometimes,co-activator and/or scavenger solution can be added in two separatestages in method (a) to (c).

Sometimes, preparation of stock solutions is not necessary. Allcomponents are mixed directly into proper pre-purified solvent. Onemethod [method (d)] to prepare catalyst solution is to first addco-activator and/or scavenger to solvent, followed by addition ofmetallocene solution or solid, followed by activator solution or solid.Another method [method (e)] is to first add metallocene solution orsolid to solvent, followed by co-activator and/or scavenger, followed byactivator. Another method [method (f)] is to first add co-activatorand/or scavenger solution or liquid to solvent, followed metallocenesolution or solid, followed by activator solution or solid. Anothermethod [method (g)] is to first add co-activator and/or scavengersolution or liquid to solvent, followed activator solution or solid,followed by metallocene solution or solid. All these methods produceactive catalyst solutions. Usually, method (a) and method (d) are themost preferred methods. All solvents used in the catalyst preparationare pre-purified by passing through purifiers, which include molecularsieves and/or activated de-oxygenation catalysts. Sometimes, a smallamount of co-activator and/or scavenger tri-alkylaluminum or aluminoxaneis added to all the solvents to remove impurities.

In a preferred embodiment, the catalyst system includes a support. Thesolubility of invention catalyst precursors allows for the readypreparation of supported catalysts. To prepare uniform supportedcatalysts, the catalyst precursor preferably dissolves in the chosensolvent. The term “uniform supported catalyst” means that the catalystprecursor, the activator and or the activated catalyst approach uniformdistribution upon the support's accessible surface area, including theinterior pore surfaces of porous supports. Some embodiments of supportedcatalysts prefer uniform supported catalysts; other embodiments show nosuch preference.

Useful supported catalyst systems may be prepared by any methodeffective to support other coordination catalyst systems, effectivemeaning that the catalyst so prepared can be used for oligomerizing orpolymerizing olefin in a heterogeneous process. The catalyst precursor,activator, co-activator if needed, suitable solvent, and support may beadded in any order or simultaneously.

By one method, the activator, dissolved in an appropriate solvent suchas toluene may be stirred with the support material for 1 minute to 10hours. The total solution volume may be greater than the pore volume ofthe support, but some embodiments limit the total solution volume belowthat needed to form a gel or slurry (about 90% to 400%, preferably about100-200% of the pore volume). The mixture is optionally heated from30-200° C. during this time. The catalyst precursor may be added to thismixture as a solid, if a suitable solvent is employed in the previousstep, or as a solution. Or alternatively, this mixture can be filtered,and the resulting solid mixed with a catalyst precursor solution.Similarly, the mixture may be vacuum-dried and mixed with a catalystprecursor solution. The resulting catalyst mixture is then stirred for 1minute to 10 hours, and the supported catalyst is filtered from thesolution and the solvent removed, either by vacuum-drying or evaporationalone.

Alternatively, the catalyst precursor and activator may be combined insolvent to form a solution. Then the support is added, and the mixtureis stirred for 1 minute to 10 hours. The total solution volume may begreater than the pore volume of the support, but some embodiments limitthe total solution volume below that needed to form a gel or slurry(about 90% to 400%, preferably about 100-200% of the pore volume). Afterstirring, the residual solvent is removed under vacuum, typically atambient temperature and over 10-16 hours. But greater or lesser timesand temperatures are possible.

The catalyst precursor may also be supported absent the activator; inthat case, the activator (and co-activator if needed) is added to aslurry process's liquid phase. For example, a solution of catalystprecursor may be mixed with a support material for a period of about 1minute to 10 hours. The resulting precatalyst mixture may be filteredfrom the solution and dried under vacuum, or evaporation alone removesthe solvent. The total catalyst-precursor-solution volume may be greaterthan the support's pore volume, but some embodiments limit the totalsolution volume below that needed to form a gel or slurry (about 90% to400%, preferably about 100-200% of the pore volume).

Additionally, two or more different catalyst precursors may be placed onthe same support using any of the support methods disclosed above.Likewise, two or more activators or an activator and co-activator may beplaced on the same support.

Suitable solid particle supports are typically comprised of polymeric orrefractory oxide materials, each being preferably porous. Any supportmaterial that has an average particle size greater than 10 μm issuitable for use in this invention. Various embodiments select a poroussupport material, such as for example, talc, inorganic oxides, inorganicchlorides, for example magnesium chloride and resinous support materialssuch as polystyrene polyolefin or polymeric compounds or any otherorganic support material and the like. Some embodiments select inorganicoxide materials as the support material including Group-2, -3, -4, -5,-13, or -14 metal or metalloid oxides. Some embodiments select thecatalyst support materials to include silica, alumina, silica-alumina,and their mixtures. Other inorganic oxides may serve either alone or incombination with the silica, alumina, or silica-alumina. These aremagnesia, titania, zirconia, and the like. Lewis acidic materials suchas montmorillonite and similar clays may also serve as a support. Inthis case, the support can optionally double as an activator component.But additional activator may also be used. In some cases, a specialfamily of solid support commonly known as MCM-41 can also be used.MCM-41 is a new class of unique crystalline support and can be preparedwith tunable pore size and tunable acidity when modified with a secondcomponent. A detailed description of this class of material and theirmodification can be found in U.S. Pat. No. 5,264,203.

The support material may be pretreated by any number of methods. Forexample, inorganic oxides may be calcined, chemically treated withdehydroxylating agents such as aluminum alkyls and the like, or both.

As stated above, polymeric carriers will also be suitable in accordancewith the invention, see for example the descriptions in WO 95/15815 andU.S. Pat. No. 5,427,991. The methods disclosed may be used with thecatalyst compounds, activators or catalyst systems of this invention toadsorb or absorb them on the polymeric supports, particularly if made upof porous particles, or may be chemically bound through functionalgroups bound to or in the polymer chains.

Useful catalyst carriers may have a surface area of from 10-700 m²/g,and or a pore volume of 0.1-4.0 cc/g and or an average particle size of10-500 μm. Some embodiments select a surface area of 50-500 m²/g, and ora pore volume of 0.5-3.5 cc/g, and or an average particle size of 20-200μm. Other embodiments select a surface area of 100-400 m²/g, and or apore volume of 0.8-3.0 cc/g, and or an average particle size of 30-100μm. Carriers of this invention typically have a pore size of 10-1000angstroms, alternatively 50-500 angstroms, or 75-350 angstroms.

The metallocenes and or the metallocene/activator combinations aregenerally deposited on the support at a loading level of 10-100micromoles of catalyst precursor per gram of solid support; alternately20-80 micromoles of catalyst precursor per gram of solid support; or40-60 micromoles of catalyst precursor per gram of support. But greateror lesser values may be used provided that the total amount of solidcatalyst precursor does not exceed the support's pore volume.

The metallocenes and or the metallocene/activator combinations can besupported for bulk, or slurry polymerization, or a fixed bed reactor orotherwise as needed. Numerous support methods are known for catalysts inthe olefin polymerization art, particularly aluminoxane-activatedcatalysts; all are suitable for use herein. See, for example, U.S. Pat.Nos. 5,057,475 and 5,227,440. An example of supported ionic catalystsappears in WO 94/03056. U.S. Pat. No. 5,643,847 and WO 96/04319A whichdescribe a particularly effective method. Both polymers and inorganicoxides may serve as supports, see U.S. Pat. Nos. 5,422,325, 5,427,991,5,498,582 and 5,466,649, and international publications WO 93/11172 andWO 94/07928.

In another preferred embodiment, the metallocene and or activator (withor without a support) are combined with an alkyl aluminum compound,preferably a trialkyl aluminum compound, prior to entering the reactor.Preferably the alkyl aluminum compound is represented by the formula:R₃Al, where each R is independently a C₁ to C₂₀ alkyl group, preferablythe R groups are independently selected from the group consisting ofmethyl, ethyl, propyl, isopropyl, butyl, isobutyl, n-butyl, pentyl,isopentyl, n-pentyl, hexyl, isohexyl, n-hexyl, heptyl, octyl, isocotyl,n-octyl, nonyl, isononyl, n-nonyl, decyl, isodecyl, n-cecyl, undecyl,isoundecyl, n-undecyl, dodecyl, isododecyl, and n-dodecyl, preferablyisobutyl, n-octyl, n-hexyl, and n-dodecyl. Preferably the alkyl aluminumcompound is selected from tri-isobutyl aluminum, tri n-octyl aluminum,tri-n-hexyl aluminum, and tri-n-dodecyl aluminum.

Polymerization Process

Many polymerization/oligomerization processes and reactor types used formetallocene-catalyzed polymerization or oligomerization such assolution, slurry, or bulk polymerization or oligomerization processescan be used in this invention. In another embodiment, if a solid orsupported catalyst is used, a slurry or continuous fixed bed or plugflow process is suitable. In a preferred embodiment, the monomers arecontacted with the metallocene compound and the activator in thesolution phase, bulk phase, or slurry phase, preferably in a continuousstirred tank reactor, continuous tubular reactor, a semi-continuousreactor, or a batch reactor. In a preferred embodiment, the temperaturein any reactor used herein is from −10° C. to 250° C., preferably from30° C. to 220° C., preferably from 50° C. to 180° C., preferably from60° C. to 170° C. In a preferred embodiment, the pressure in any reactorused herein is from 0.1 to 100 atmospheres, preferably from 0.5 to 75atmospheres, preferably from 1 to 50 atmospheres. In another embodiment,the monomers, metallocene and activator are contacted for a residencetime of from 1 second to 100 hours, preferably 30 seconds to 50 hours,preferably 2 minutes to 6 hours, preferably 1 minute to 4 hours. Inanother embodiment solvent or diluent is present in the reactor and ispreferably selected from the group consisting of butanes, pentanes,hexanes, heptanes, octanes, nonanes, decanes, undecanes, dodecanes,tridecanes, tetradecanes, pentadecanes, hexadecanes, benzene, toluene,o-xylenes, m-xylenes, p-xylenes, ethylbenzene, isopropylbenzene, andn-butylbenzene, preferably toluene and or xylenes and or ethylbenzene,Norpar™ or Isopar™ solvent. These solvents or diluents may bepre-treated in same manners as the feed olefins.

Typically in the processes of this invention, one or more transitionmetal compounds, one or more activators, and one or more feeds accordingto the present invention are contacted to produce polymer or oligomer.These catalysts may be supported and as such will be particularly usefulin the known slurry, solution, or bulk operating modes conducted insingle, series, or parallel reactors. If the catalyst or activator orco-activator is a soluble compound, the reaction can be carried out in asolution mode. Even if one of the components is not completely solublein the reaction medium or in the feed solution, either at the beginningof the reaction or during or at the later stage of the reaction, asolution or slurry type operation is still applicable. In any case, thecatalyst components in solvents, such as toluene or other convenientlyavailable aromatic solvents, or in aliphatic solvent, or in the feedalpha-olefin stream are fed into the reactor under inert atmosphere(usually nitrogen or argon blanketed atmosphere) to allow the reactionto take place. In this process, the feed alpha-olefins can be chargedindividually or pre-mixed in a mixture, or one stream contains mixtureof feed olefins and another stream contains one olefin feed, such as inthe case when one of the feed olefins is gaseous or liquefied gaspropylene or 1-butene or mixed butene stream. The reaction can be run ina batch mode where all the components are added into a reactor andallowed to react to a pre-designed degree of conversion, either partialconversion or full conversion. Then the catalyst is deactivated by anypossible means, such as exposure to air, water, or by addition ofalcohols or solvents containing deactivator agents. The reaction canalso be carried out in a semi-continuous operation, where feeds andcatalyst components are continuously and simultaneously added to thereactor so to maintain a constant ratio of catalyst system and feedolefins. When all feeds and catalyst components are added, the reactionis allowed to proceed to a pre-determined stage. Then the reaction isdiscontinued in the same manner as described in the batch operation. Thereaction can also be carried out in a continuous operation, where feedsand catalyst are continuously and simultaneously added to the reactor soto maintain a constant ratio of catalyst system and feed olefins. Thereaction product is continuously withdrawn from the reactor, as in atypical continuous stirred tank reactor (CSTR) operation. The residencetimes of the reactants are controlled by a pre-determined degree ofconversion. The withdrawn product is then typically quenched in theseparate reactor in a similar manner as other operation. In a preferredembodiment, any of the processes to prepare PAO's described herein arecontinuous processes. Preferably the continuous process comprises thesteps of a) continuously introducing a feed stream comprising at least10 mole % of the one or more C₃ to C₂₄ alpha-olefins into a reactor, b)continuously introducing the metallocene compound and the activator intothe reactor, and c) continuously withdrawing the polyalpha-olefin fromthe reactor. In another embodiment, the continuous process comprises thestep of maintaining a partial pressure of hydrogen in the reactor of 200psi (1379 kPa) or less, based upon the total pressure of the reactor,preferably 150 psi (1034 kPa) or less, preferably 100 psi (690 kPa) orless, preferably 50 psi (345 kPa) or less, preferably 25 psi (173 kPa)or less, preferably 10 psi (69 kPa) or less.

One or more reactors in series or in parallel may be used in the presentinvention. The transition metal compound, activator and when required,co-activator, may be delivered as a solution or slurry in a solvent orin the alpha-olefin feed stream, either separately to the reactor,activated in-line just prior to the reactor, or preactivated and pumpedas an activated solution or slurry to the reactor.Polymerizations/oligomerizations are carried out in either singlereactor operation, in which monomer, or several monomers,catalyst/activator/co-activator, optional scavenger, and optionalmodifiers are added continuously to a single reactor or in seriesreactor operation, in which the above components are added to each oftwo or more reactors connected in series. The catalyst components can beadded to the first reactor in the series. The catalyst component mayalso be added to both reactors, with one component being added to firstreaction and another component to other reactors. In one preferredembodiment, the precatalyst is activated in the reactor in the presenceof olefin. In another embodiment, the precatalyst such as the dichlorideform of the metallocenes is pre-treated with alkylalumum reagents,especially, triisobutylaluminum, tri-n-hexylaluminum ortri-n-octylaluminum, followed by charging into the reactor containingother catalyst component and the feed olefins, or followed bypre-activation with the other catalyst component to give the fullyactivated catalyst, which is then fed into the reactor containing feedolefins. In another alternative, the pre-catalyst metallocene is mixedwith the activator and/or the co-activator and this activated catalystis then charged into reactor, together with feed olefin streamcontaining some scavenger or co-activator. In another alternative, thewhole or part of the co-activator is pre-mixed with the feed olefins andcharged into the reactor at the same time as the other catalyst solutioncontaining metallocene and activators and/or co-activator. The catalystcompositions can be used individually or can be mixed with other knownpolymerization catalysts to prepare polymer or oligomer blends. Monomerand catalyst selection allows polymer or oligomer blend preparationunder conditions analogous to those using individual catalysts. Polymershaving increased MWD are available from polymers made with mixedcatalyst systems can thus be achieved.

Generally, when using metallocene catalysts, it is important topre-treat the feed components to remove any impurities in olefins,solvents, or diluents or the inert gases (nitrogen or argon) used toblanket the reactor. The feed pre-treatment is usually conducted bypassing the liquid or gaseous feed stream over at least one bed ofactivated molecular sieves, such as 13×, 5 A, 4 A, 3 A molecular sieve.Sometimes, two beds of the same or different molecular sieves are used.Sometimes, a special oxygenate removal catalyst bed is also employed.Such oxygenate removal catalysts include various reduced copper oxidecatalyst or reduced copper chromite catalyst. After carefulpre-treatment of feed olefins, solvents, diluents and after carefulprecaution to keep the catalyst component stream(s) and reactor free ofany impurities, as would be recognized by one of ordinary skill in theart, the reaction should proceed well. In a preferred embodiment,particularly in the case where the metallocene catalyst is immobilizedon a support, the complete catalyst system will additionally compriseone or more scavenging compounds. Here, the term scavenging compoundmeans a compound that removes polar impurities from the reactionenvironment. These impurities adversely affect catalyst activity andstability. Typically, purifying steps are used before introducingreaction components to a reaction vessel. But such steps will rarelyallow polymerization or oligomerization without using some scavengingcompounds. Normally, the polymerization process will still use at leastsmall amounts of scavenging compounds.

Typically, the scavenging compound will be an organometallic compoundsuch as the Group-13 organometallic compounds of U.S. Pat. Nos.5,153,157, 5,241,025 and WO-A-91/09882, WO-A-94/03506, WO-A-93/14132,and that of WO 95/07941. Exemplary compounds include triethyl aluminum,triethyl borane, tri-iso-butyl aluminum, diisobutylaluminum hydride,methyl aluminoxane, iso-butyl aluminoxane, and tri-n-octyl aluminum.Those scavenging compounds having bulky or C₆-C₂₀ linear hydrocarbylsubstituents connected to the metal or metalloid center usually minimizeadverse interaction with the active catalyst. Examples includetriethylaluminum, but more preferably, bulky compounds such astri-iso-butyl aluminum, tri-iso-prenyl aluminum, and long-chain linearalkyl-substituted aluminum compounds, such as tri-n-hexyl aluminum,tri-n-octyl aluminum, or tri-n-dodecyl aluminum. When aluminoxane isused as the activator, any excess over that needed for activation willscavenge impurities and additional scavenging compounds may beunnecessary. Aluminoxanes also may be added in scavenging quantitieswith other activators, e.g., methylaluminoxane, [Me₂HNPh]⁺[B(pfp)₄]⁻ orB(pfp)₃, where pfp is perfluorophenyl (C₆F₅) Me is methyl and Ph isphenyl.

The process according to the invention may also be accomplished in ahomogeneous solution processes. Generally this involves polymerizationor oligomerization in a continuous reactor in which the polymer formedand the starting feed according to the invention and catalyst materialsaccording to the invention are agitated to reduce or avoid concentrationor temperature gradients. Temperature control in the reactor isgenerally obtained by balancing the heat of polymerization and withreactor cooling by reactor jackets or cooling coils or a cooledside-stream of reactant to cool the contents of the reactor, autorefrigeration, pre-chilled feeds, vaporization of liquid medium(diluent, monomers or solvent) or combinations of all the above methods.Adiabatic reactors with pre-chilled feeds may also be used. The reactortemperature depends on the catalyst used and the product desired. Highertemperatures tend to give lower molecular weights and lower temperaturestend to give higher molecular weights, however this is not a hard andfast rule. In general, the reactor temperature preferably can varybetween about 0° C. and about 300° C., more preferably from about 10° C.to about 250° C., and most preferably from about 25° C. to about 230° C.Usually, it is important to control the reaction temperature aspre-determined. In order to produce fluids with narrow moleculardistribution, such as to promote the highest possible shear stability,it is useful to control the reaction temperature to obtain minimum oftemperature fluctuation in the reactor or over the course of thereaction time. If multiple reactors are used in series or in parallel,it is useful to keep the temperature constant in a pre-determined valueto minimize any broadening of molecular weight distribution. In order toproduce fluids with broad molecular weight distribution, one can adjustthe reaction temperature swing or fluctuation, or as in seriesoperation, the second reactor temperature is preferably higher than thefirst reactor temperature. In parallel reactor operation, thetemperatures of the two reactors are independent. Or one can use twotypes of metallocene catalysts.

While reaction conditions may generally be determined by one of ordinaryskill in the art in possession of the present disclosure, typicalconditions will now be discussed.

The pressure in any reactor used herein can vary typically from about0.1 atmosphere to 100 atmosphere (1.5 psi to 1500 psi), preferably from0.5 bar to 75 atm (8 psi-1125 psi), most preferably from 1.0 to 50 atm(15 psi to 750 psi). The reaction pressure is usually higher thanatmospheric pressure when light olefins with high vapor pressures, suchas propylene or butenes, are used as one of the feed olefins. Thereaction can be carried out under the atmosphere of nitrogen or withsome hydrogen. Sometimes a small amount of hydrogen is added to thereactor to improve the catalyst productivity. The amount of hydrogen ispreferred to keep at such a level to improve catalyst productivity, butnot induce any hydrogenation of olefins, especially the feedalpha-olefins because the conversion of alpha-olefins into saturatedparaffins is very detrimental to the efficiency of the process. Theamount of hydrogen partial pressure is preferred to be kept low, lessthan 100 psi, preferably less than 50 psi, preferably less than 25 psi,preferably less than 10 psi, preferably less than 5 psi, preferably lessthan 1 psi. In a particularly preferred embodiment in any of the processdescribed herein the concentration of hydrogen in the reactant phase isless than 100 ppm, preferably less than 50 ppm, preferably less than 10ppm, preferably less than 1 ppm. In a particularly preferred embodimentin any of the process described herein the concentration of hydrogen inthe reactor is kept at a partial pressure of 200 psi (1379 kPa) or less,based upon the total pressure of the reactor, preferably 150 psi (1034kPa) or less, preferably 100 psi (690 kPa) or less, preferably 50 psi(345 kPa) or less, preferably 10 psi (69 kPa) or less.

The reaction time or reactor residence time is usually dependent on thetype of catalyst used, the amount of catalyst system used, and thedesired conversion level. Different metallocenes have differentactivity. Usually, higher degree of alkyl substitution on thecyclopentadienyl ring, or bridging improves catalyst productivity.Catalysts such as 1,2,3,4-tetramethylcyclopentadienylzirconiumdichloride or 1,2,4-tri methylcyclopentadienylzirconium dichloride, orpentamethylcyclopentadienyl zirconium dichloride or their dialkylanalogs have desirable high productivity and stability thanunsubstituted metallocenes. Certain bridged and bridged withsubstitution catalysts, such as the di-halides or dialkyls ofdimethylsilylbis[cyclopentadienyl]zirconium,dimethylsilylbis[indenyl]zirconium ordimethylsilylbis[tetrahydro-indenyl]zirconium,dimethylsilylbis[1-methylindenyl]zirconium,ethylidenebis[indenyl]zirconium,ethylidenebis[tetrahydroindenyl]zirconium,ethylidenebis[1-methylindenyl]zirconium, or their hafnium analogs, etc.Usually the amount of catalyst components used is determinative. A highcatalyst loading tends to gives high conversion at short reaction time.However, high catalyst usage makes the production process uneconomicaland difficult to manage the reaction heat or to control the reactiontemperature. Therefore, it is useful to choose a catalyst with maximumcatalyst productivity to minimize the amount of metallocene and theamount of activators needed. When the catalyst system is metalloceneplus methylaluminoxane, the range of methylaluminoxane used is typicallyin the range of 0.01 milligram (mg) to 500 mg/g of alpha-olefin feed. Amore preferred range is from 0.02 mg to 10 mg/g of alpha-olefin feed.Furthermore, the molar ratios of the aluminum to metallocene (Al/M molarration) range from 2 to 4000, preferably 10 to 2000, more preferably 50to 1000, and most preferably 100 to 500. When the catalyst system ismetallocene plus a Lewis acid or an ionic promoter with NCA component,the metallocene use is typically in the range of 0.01 microgram to 500micrograms of metallocene component/gram of alpha-olefin feed. Usuallythe preferred range is from 0.1 microgram to 100 microgram ofmetallocene component per gram of alpha-olefin feed. Furthermore, themolar ratio of the NCA activator to metallocene is in the range from 0.1to 10, preferably 0.5 to 5, more preferably 0.5 to 3. If a co-activatorof alkylaluminum compound is used, the molar ratio of the Al tometallocene is in the range from 1 to 1000, preferably 2 to 500, morepreferably 4 to 400, even more preferably 4 to 100, or most preferably10 to 50.

Typically, the highest possible conversion (close to 100%) of feedalpha-olefin in the shortest possible reaction time is preferred.However, in CSTR operation, it is sometimes optimal to run the reactionat slightly less than 100% conversion. There are also occasions whenpartial conversion is more desirable, namely when the narrowest possibleMWD of the product is desirable because partial conversion can avoid aMWD broadening effect. Typically, the conversions of the total feedolefins are in the range of 20% to 100%, more desirably in the range of50% to 100%, and most desirably in the range of 80 to 99%. If thereaction is conducted to less than 100% conversion of the alpha-olefin,the unreacted starting material after separation from other product andsolvents/diluents can be recycled to increase the total processefficiency. When the catalyst system is metallocene and MAO, thecatalyst productivity is usually in the range of 20 to 50,000 gram totalproduct per gram of MAO, preferably greater than 100 gram total productper gram of MAO, most preferably greater than 500 gram total product pergram of MAO. When the catalyst is metallocene and a Lewis acid or anionic promoter with NCA component, the catalyst productivity istypically 1000 to 10,000,000 gram total product per gram of metallocenecatalyst, preferably 10,000 gram, more preferably 50,000 gram of totalproduct per gram of metallocene catalyst. The catalyst productivity isin the same range for grams of total product per grams of Lewis acid orionic promoter with NCA component.

Desirable residence times for any process described herein may likewisebe determined by one of ordinary skill in the art in possession of thepresent disclosure, and will typically range from 1 minute to 20 hours,or more typically 5 minutes to 10 hours.

Each of these processes may also be employed in single reactor, parallelor series reactor configurations. The liquid processes comprisecontacting olefin monomers with the above described catalyst system,preferably in a suitable diluent, solvent, recycle, or mixture thereof,and allowing the reaction to occur for a sufficient time to produce thedesired polymers or oligomers. Hydrocarbon solvents both aliphatic andaromatic are suitable. Aromatics such as benzene, toluene, xylenes,ethylbenzene, propylbenzene, cumene, t-butylbenzene are suitable.Alkanes, such as hexane, heptane, pentane, isopentane, and octane,Norpar™ fluids or Isopar fluids from ExxonMobil Chemical Company inHouston, Tex. are also suitable. Generally, toluene is most suitable todissolve catalyst components. Norpar fluids or Isopar fluids or hexanes(or mixtures thereof) are preferred as reaction diluents. Oftentimes, amixture of toluene and Norpar fluids or Isopar fluids is used as diluentor solvent.

The process can be carried out in a continuous stirred tank reactor,batch reactor, or plug flow reactor, or more than one reactor operatedin series or parallel. These reactors may have or may not have internalcooling and the monomer feed may or may not be refrigerated. See, forinstance, U.S. Pat. No. 5,705,577 for typical process conditions.

When a solid supported catalyst is used for the conversion, a slurrypolymerization/oligomerization process generally operates in the similartemperature, pressure and residence time range as described previously.In a slurry polymerization or oligomerization, a suspension of solidcatalyst, promoters, monomer and comonomers are added. The suspensionincluding diluent is intermittently or continuously removed from thereactor. The catalyst is then separated from the product by filtration,centrifugation, or settlement. The fluid is then distilled to removesolvent, any unreacted components, and light product. A portion or allof the solvent and unreacted component or light components can berecycled for reuse.

If the catalyst used is un-supported, solution catalyst, when thereaction is complete as in the batch mode, or when the product iswithdrawn from the reactor as in a CSTR, the product may still containsoluble or suspended catalyst components. These components arepreferably deactivated and/or removed. Any of the usual catalystdeactivation methods or aqueous wash methods can be used to remove thecatalyst component. Typically, the reaction is deactivated by additionof stoichiometric amount or excess of air, moisture, alcohol,isopropanol, etc. The mixture is then washed with dilute sodiumhydroxide or with water to remove catalyst components. The residualorganic layer is then subjected to distillation to remove solvent, whichcan be recycled for reuse. The distillation can further remove any lightreaction product from C₁₈ and less. These light components can be usedas diluent for further reaction. Or they can be used as olefinic rawmaterial for other chemical synthesis, as these light olefin producthave vinylidene unsaturation, most suitable for furtherfunctionalization to convert in high performance fluids. Or these lightolefin products can be hydrogenated to be used as high qualityparaffinic solvents.

Polymerization or oligomerization in absence of hydrogen is alsoadvantageous to provide polymers or oligomers with high degree ofunsaturated double bonds. These double bonds can be easily convertedinto functionalized fluids with multiple performance features. Examplesfor converting these polymers with molecular weight greater than 300 canbe found in the preparation of ashless dispersants, by reacting thepolymers with maleic anhydride to give PAO-succinic anhydride which canthen reacted with amines, alcohols, polyether alcohols to convert intodispersants. Examples for such conversion can be found in the book“Lubricant Additives: Chemistry and Application,” ed. by Leslie R.Rudnick, p. 143-170.

In a typical process to produce high performance fluids from mixed LAOover metallocene catalyst system, the polymerization step usuallyproduces some light ends with less than C₂₄ carbons. The amount of thelight fraction usually depends on the reaction temperature, catalystused, residence time, and the desired fluid viscosity or molecularweight. Usually, a lower viscosity process produces higher amount oflight fraction and high viscosity (>10 cSt) process produces almostexclusively >C₂₄ fraction, with little or no light fractions. Forexample, the light fraction can range from 0.1 wt % to 30 wt % of totalproduct for a 150 cSt fluid to 6 cSt fluid, respectively, from mixedLAO. It is usually more desirable to produce the least amount of lightfraction. The amount of light fraction can be minimized by carefulcontrol of the process temperature, residence time, stable andhomogeneous catalyst, etc.

Polymerization can also be carried out in the presence of hydrogen. Theadvantages of polymerization in the presence of H₂ are increasedcatalyst productivity and reduced degree of unsaturation, which underproper conditions can be so low that no further hydrogenation step isneeded. When the reaction is carried out in the presence of hydrogen,hydrogen pressure is advantageously kept low to achieve highestproductivity. High hydrogen pressure will have the disadvantage ofhydrogenating the alpha-olefins into alkanes, thus reducing the totalproduct yields. Typically, hydrogen partial pressure should be keptbelow 200 psi, preferably below 50 psi more preferably below 30 psi ormost preferably below 20 psi. In a static, batch operation, the molarratio of olefins to hydrogen is advantageously kept below 5, preferablybelow 10, more preferably below 20, or most preferably below 50. One ofordinary skill in the art in possession of the present disclosure candetermine the appropriate hydrogen level without more than routineexperimentation.

The polyalpha-olefins produced from the above polymerization processusing a mixed alpha-olefins as feed contain unsaturated double bond,sometimes rich in vinylidene contents with some 1,2-disubstitutedolefins. These unsaturated polymers are most suitable for furtherfunctionalization reaction. Examples of such functionalization arealkylation with aromatics compounds, such as benzene, toluene, xylene,naphthalene, phenol or alkylphenols. The polymer olefins can also reactwith maleic anhydride to give polyalpha-olefin succinic anhydride, whichcan be further converted with amines or alcohols to correspondingsuccinimide or succinate esters. These imides and esters are superiordispersants. Because of the use of PAO as the hydrocarbon moiety, thefinished dispersant will have much better viscometrics than theconventional dispersants made from polyisobutylene.

In an embodiment, the product of the process according to the invention,comprising polyalpha-olefins, is hydrogenated. In particular thepolyalpha-olefin product is preferably treated to reduce heteroatomcatalyst components to less than 600 ppm, and then contacted withhydrogen and a hydrogenation catalyst to produce a polyalpha-olefinhaving a bromine number less than 1.8. Usually, the bromine number isbelow 1.8. Lower bromine number is more desirable, as it indicates animproved thermal/oxidative stability. In a preferred embodiment, thetreated polyalpha-olefin comprises 100 ppm of heteroatom catalystcomponents or less, preferably 10 ppm of heteroatom catalyst componentsor less. Preferably the hydrogenation catalyst is selected from thegroup consisting of supported Group 7, 8, 9, and 10 metals, preferablythe hydrogenation catalyst selected from the group consisting of one ormore of Ni, Pd, Pt, Co, Rh, Fe, Ru, Os, Cr, Mo, and W, supported onsilica, alumina, clay, titania, zirconia, or mixed metal oxide supports.A preferred hydrogenation catalyst is nickel supported on kieselguhr, orplatinum or palladium supported on alumina, or cobalt-molydenumsupported on alumina. Usually, a high nickel content catalyst, such as60% Ni on Keiselguhr catalyst is used, or a supported catalyst with highamount of Co—Mo loading.

In a preferred embodiment the polyalpha-olefin product is contacted withhydrogen and a hydrogenation catalyst at a temperature from 25 to 350°C., preferably 100 to 300° C. In another preferred embodiment thepolyalpha-olefin is contacted with hydrogen and a hydrogenation catalystfor a time period from 5 minutes to 100 hours, preferably from 5 minutesto 24 hours. In another preferred embodiment the polyalpha-olefin iscontacted with hydrogen and a hydrogenation catalyst at a hydrogenpressure of from 25 psi to 2500 psi, preferably from 100 to 2000 psi. Inanother preferred embodiment the hydrogenation process reduces thenumber of mm triad groups in a polyalpha-olefin by 1 to 80%.Hydrogenation of PAO's per se is well-known. See, for instance, U.S.Pat. No. 5,573,657 and “Lubricant Base Oil Hydrogen Refining Processes”(page 119 to 152) in Lubricant Base Oil and Wax Processing, by AvilinoSequeira, Jr., Marcel Dekker, Inc., NY, 1994.

The hydrogenation process can be accomplished in a slurry reactor in abatch operation or in a continuous stirred tank reactor (CSTR), wherethe catalyst concentration is 0.001 wt % to 20 wt % of the PAO (orHVI-PAO) product, or preferably 0.01 to 10 wt % of the product. Hydrogenand feed are added continuously to the reactor to allow for a certainresidence time, usually 5 minutes to 10 hours, to allow completehydrogenation of the unsaturated olefins and to allow proper conversion.The amount of catalyst added is usually in slight excess, to compensatefor the catalyst deactivation. The catalyst and hydrogenated PAO and/orHVI-PAO are continuously withdrawn from the reactor. The product mixturewas then filtered, centrifuged or settled to remove the solidhydrogenation catalyst. The catalyst can be regenerated and reused. Thehydrogenated PAO can be used as is or further distilled or fractionatedto the right component if necessary. In some cases, when thehydrogenation catalyst show no catalyst deactivation over long termoperation, the stir tank hydrogenation process can be carried out in amanner where a fixed amount of catalyst is maintained in the reactor,usually 0.1 wt % to 10% of the total reactant, and only hydrogen and PAOfeed are continuously added at certain feed rate and only hydrogenatedPAO was withdrawn from the reactor.

The hydrogenation process can also be accomplished by a fixed bedprocess, in which the solid catalyst is packed inside a tubular reactorand heated to reactor temperature. Hydrogen and PAO and/or HVI-PAO feedcan be fed through the reactor simultaneously from the top or bottom orcountercurrently to maximize the contact between hydrogen, PAO/HVI-PAOand catalyst, and to allow best heat management. The feed rate of thePAO and hydrogen are adjusted to give proper residence to allow completehydrogenation of the unsaturated olefins in the feed and to allowdesirable conversion of mm triads in the process. The hydrogenated PAOfluid can be used as is or further distilled or fractionated to give theright component, if necessary.

Polymer Product Composition.

This invention provides a liquid polyalpha-olefin composition which inembodiments may be characterized as comprising at least two types ofbranches with average branch length of at least 2.1, ranging from 2.1 to12, preferably 3 to 11, more preferably 4 to 10, more preferably 4.5 to9.5, more preferably 5 to 9, more preferably 5.5 to 8.5, more preferably6 to 8, and most preferably 7 to 8. The product is a liquid. For thepurposes of this invention, a “liquid” is defined to be a fluid that hasno distinct melting point above 0° C., preferably no distinct meltingpoint above −20° C., and has a kinematic viscosity at 100° C. of 3000cSt or less, preferably 1000 cSt or less and/or a kinematic viscosity at40° C. of 35,000 cSt or less, preferably 10,000 cSt or less.

The polymers may be further characterized as having a random monomerdistribution along the polymer backbone. This randomness can becharacterized by either nuclear magnetic resonance spectroscopy (NMR) ormass spectrometry (MS) methods or by gas chromotagraphic (GC) analysisof light oligomer fractions.

In MS, the degree of randomness (χ) is defined as the sum of MarkovianP-matrix elements, χ=P_(AB)+P_(BA), where A and B are comonomers orcombination of comonomers (see reference Mass Spectrometry of Polymers,edited by G. Montaudo and R. P. Lattimer, CRC Press, Boca Raton, Fla.,2002, Chapter 2, p. 72 to 85). For an ideal random copolymer χ=1. χ forthis inventive polymer is usually between 0.7 to 1.4, preferably between0.8 to 1.2, preferably between 0.9 and 1.1. The MS method is carried outas following. MS technique is based on a combination of field desorptionmass spectrometry (FDMS) and Markovian statistics. In FDMS, samples aredissolved in methylene chloride with 0.1 to 10% (w/v) concentration. 1to 5 μl of the solution is deposited on to the FD emitter. The emitterwas inserted into the ion source of a mass spectrometer in 10⁻⁵ to 10⁻⁶torr vacuum. A high electric voltage (10 to 13 kV) is applied betweenthe emitter and a pair of extraction rod. A high field strength of 10⁷to 10⁸ v/cm can be reached. One or more electrons were removed from themolecules via a quantum tunneling effect. Vibration excitation isminimal and thus intact molecular ions are formed, generating molecularion mass spectra for the PAO oligomers. Markovian statistics weredeveloped to calculate PAO oligomer distributions based on transitionprobability matrix (P-matrix). A theoretical mass spectrum wasdetermined by summation of all oligomer distribution and was comparedagainst the experimental mass spectrum in the molecular weight rangebetween 10 to 10,000 g/mol, preferably between 100 to 5000 g/mol,preferably between 400 and 1000 g/mol. The P-matrix was adjusted in aniterative process to minimize the differences between the theoreticaland experimental mass spectral data. The product composition andstructure (degree of randomness) can then be calculated from theoptimized P-matrix elements. Other parameters such as run length andfeed reactivity ratio can also be deduced from the Markovian statistics.For product described in this invention, zero order Markovian (orBernoullian random) distribution showed the best fit with experimentaldata with χ ranges from 0.93 to 1.05.

The NMR method to characterize the material is described below.

Typically, proton NMR spectroscopy—because of its intrinsically limitedspectral dispersion—provides decreasing utility for determining thecomposition of the polymers as the lengths of the comonomers increase.The greater resolution in the carbon spectra often provides multipleopportunities for determining the monomer composition. For example, inpolymerizations of 1-butene with comonomers longer than or equal to C₁₀,we calculated the composition in two ways: the 1B₂ (10.7 ppm) and 1B₃₊(14.1 ppm) methyl resonances, and the backbone S_(αα) methylenes betweenthe branches. The methyl integral calculation is a direct measurementfrom the peak integrals, and may suffer from endgroup errors (e.g.initiating butenes would appear in the comonomer region). The S_(αα)methylene region (41-39 ppm), while also susceptible to end groupeffects in low molecular weight materials, shows three S_(αα) methylenepeaks that were assigned to the C_(n)-C_(n), C_(n)-C₄, and C₄-C₄structures. The integrals of the three peaks were fit by least squaresminimization to a Bernoullian model for monomer addition. TheBernoullian model defines the likelihood of finding a specific monomerat any position in the chain as proportional to the overall molarconcentration of that monomer and independent of the identity ofneighboring monomers. The excellent fit of the S_(αα) methylene peakareas with Bernoullian distribution indicates very little deviation fromrandom monomer addition. The adjustable parameter for the fits is themole-percentage C₄, which can be converted to a weight-percentage. Thefitting process is carried out by normalizing the sum of the S_(αα)methylene integrals to 1.0. Least squares minimization seeks to minimizethe square root of the sum of the squares (Diff) of the differencesbetween the experimental dyad mole fractions (e.g. [AA]_(exp)) and themole fractions predicted by the Bernoullian model (e.g. [AA]_(Bern)),where the two comonomers in the polymer are A and B. The formula forDiff is given below.

${Diff} = \sqrt{\begin{matrix}{\left( {\lbrack{AA}\rbrack_{{ex}\; p} - \lbrack{AA}\rbrack_{Bern}} \right)^{2} + \left( {\left\lbrack {{AB} + {BA}} \right\rbrack_{{ex}\; p} -} \right.} \\{\left. \left\lbrack {{AB} + {BA}} \right\rbrack_{Bern} \right)^{2} + \left( {\lbrack{BB}\rbrack_{{ex}\; p} - \lbrack{BB}\rbrack_{Bern}} \right)^{2}}\end{matrix}}$

In cases where multiple LAOs are used, and signals from longer LAO's arenot resolved, analysis can be performed with the non-resolved monomerslumped into an aggregate A and/or an aggregate B monomer, depending onwhere their resonances appear. The minimized Diff will then address therandomness of aggregate A versus aggregate B.

When the feed composition contains more than two alpha-olefins, theanalytical method and mathematics to analyze the data become verycomplex for both the NMR method and the MS method. In this case, one mayconsider analyzing the polymer compositional randomness by lumping thefeed olefins into two groups with averaged properties to simplify thecompositional analysis. The conclusion should be within the scope of thetwo component analysis. Another method to deduce the randomness of thepolymer composition is to analyze the rates of consumption of thestarting alpha-olefins during polymerization. The relative ratio of thefastest reacting monomer should not be more than 5 times faster than theslowest reacting monomer. A more preferred ratio is less than 3, and themost preferred ratio is less than 2. As a ratio of 1 usually indicates arandom copolymer, another possible method for deducing the randomness ofthe polymer composition is to calculate the ratio of the amount of onealpha-olefin in the product to the same alpha-olefin in the feed. Forthe polymers in the present invention, this ratio is within 0.5 to 3,and preferably 0.8 to 2, with the ratio of 1 as a completely randompolymer.

The gas chromatographic (GC) method can also be extended to analyzingthe whole or partial polymer composition using an internal standardmethod. The gas chromatograph is a HP model equipped with a 60 meter DB1capillary column. A 1 microliter sample was injected into the column at70° C., held for 0 minutes, program-heated at 10° C. per minute to 300°C. and held for 15 minutes. The content of the dimer, trimer, tetramerof total carbon numbers less than 50 can be analyzed quantitativelyusing the gc method. The distribution of the composition from dimer,trimer and tetramer and/or pentamer can be fit to a Bernoulliandistribution and the randomness can be calculated from the differencebetween the GC analysis and best fit calculation.

In another embodiment, any of the polyalpha-olefins described hereinhave an M_(w) (weight average molecular weight) of 100,000 or less,preferably between 200 and 80,000, more preferably between 250 and60,000, more preferably between 280 and 50,000, and most preferablybetween 336 and 40,000 g/mol. (Preferred M_(w)'s include those from 224to 55,100, preferably from 392 to 30,000, more preferably 800 to 24,000,and most preferably 2,000 to 37,5000 g/mol. Alternately preferredM_(w)'s include 224 to about 6790, and preferably 224 to about 2720).

In another embodiment, any of the alpha-olefins described hereinpreferably have a number average molecular weight (M_(n)) of 50,000 orless, more preferably between 200 and 40,000, more preferably between250 and 30,000, or most preferably between 500 and 20,000 g/mol. Morepreferred M_(n) ranges include 280 to 10,000, 280 to 4,000, 200 to20,900, 280 to 10,000, 200 to 7000, 200 to 2000, 280 to 2900, 280 to1700, and 200 to 500.

In another embodiment, any of the polyalpha-olefins described hereinpreferably have an M_(w)/M_(n) or molecular weight dispersity (MWD) ofgreater than 1 and less than 5, preferably less than 4, more preferablyless than 3, more preferably less than 2.5, and most preferably lessthan 2.

The M_(w) and M_(n) are measured by GPC method using polystyrene ascalibration standard. The M_(n) is correlated with the fluid viscosityaccording to a power equation M_(n)=A×(V)^(B), where V is kinematicviscosity measured at 100° C. according to the ASTM D 445 method, A andB are constants which vary slightly depending on the type of olefinfeeds. For example, when a set PAO made from a mixed feed of 33 wt % C₆and 67 wt % C₁₂ LAOs was analyzed by GPC, the relationship of M_(n)versus 100° C. viscosity was as follows: M_(n)=344.96×(V)^(0.4921).

In a preferred embodiment of this invention, any PAO described hereinmay have a pour point of less than 10° C. (as measured by ASTM D 97).Pour point of any fluid is usually a function of fluid viscosity. Withina class of fluids, usually high viscosity fluids have high pour points,and low viscosity fluids have low pour points. The pour point of thePAOs of this invention have pour points of less than 10° C., preferablyless than 0° C., more preferably less than −10° C., more preferably lessthan −20° C., more preferably less than −25° C., more preferably lessthan −30° C., more preferably less than −35° C., more preferably lessthan −50° C., and most preferably less than −70° C.

In a preferred embodiment of this invention, any PAO described hereinmay have a kinematic viscosity at 40° C. from about 4 to about 80,000centi-Stokes (cSt) as measured by ASTM D 445 method, preferably fromabout 5 cSt to about 50,000 cSt at 40° C.

In another embodiment according to the present invention, anypolyalpha-olefin described herein may have a kinematic viscosity at 100°C. from about 1.5 to about 5,000 centi-Stokes (cSt), preferably fromabout 2 cSt to about 3,000 cSt, more preferably from about 3 cSt toabout 1,000 cSt, and yet more preferably from about 8 cSt to about 500cSt. The PAOs have viscosities in the range of 2 to 500 cSt at 100° C.in one embodiment, and from 2 to 3000 cSt at 100° C. in anotherembodiment, and from 3.2 to 300 cS in another embodiment. (Allviscosities are measured by ASTM D 445 method at 100° C., except whenspecified at other temperatures.).

In another embodiment according to the present invention anypolyalpha-olefin described herein may have a kinematic viscosity at 100°C. from 3 to 10 cSt and a flash point of 130° C. or more (as measured bythe ASTM D 92 method).

The PAOs prepared herein, particularly those of low viscosity (such asthose with a KV₁₀₀ of 10 cSt or less), are especially suitable as basestocks for high performance automotive engine oil formulation bythemselves or by blending with other fluids, such as Group I, II, GroupII+, Group III, Group III+ (Note: Group II+ and Group III+ are namesoften used in trade journals, and thus known to one of ordinary skill inthe art; they usually denote base stocks that have properties betterthan Gr II or III, but can not fully meet the next level ofspecification; as used herein, each of the per se well know APIclassifications I through V will include their “+” basestock, ifavailable, unless the “+” basestock is specifically recited; in theclaims the “+” form is considered part of the API group denoted), orlube base stocks derived from hydroisomerization of wax fraction fromFischer-Tropsch hydrocarbon synthesis from CO/H₂ syn gas, or other GroupIV or Group V base stocks. PAOs having KV₁₀₀'s from 3 cSt to 8 cSt arealso preferred grades for high performance automotive engine oil orindustrial oil formulations. The PAOs of 40 to 1000 cS made in thisinvention and especially some high KV₁₀₀ grades up to 5000 cSt arespecially desirable for use as blend stock with Gr I, II, III, III+, IV,V, or GTL derived lube base stocks for use in industrial and automotiveengine or gear oil. They are also suitable for use in personal careapplication, such as blends with soap, detergents, other emollients, foruse in personal care cream, lotion, sticks, shampoo, detergents, etc. Inanother embodiment the PAOs have KV₁₀₀'s ranging from about 10 to about3045 cSt. In another embodiment the PAOs have KV₁₀₀'s ranging from about20 to about 1500 cSt.

In another embodiment according to the present invention anypolyalpha-olefin described herein may have a viscosity index (VI) offrom 80 to 400, alternatively from 100 to 380, alternatively from 100 to300, alternatively from 140 to 380, alternatively from 180 to 306,alternatively from 252 to 306, alternatively the viscosity index is atleast about 165, alternatively at least about 187, alternatively atleast about 200, alternatively at least about 252. VI usually is afunction of fluid viscosity. For many lower viscosity (KV₁₀₀ of 3 to 10cSt) fluids made from 1-decene equivalent feeds, the preferred VI rangeis from 100 to 180. Other embodiments include ranges from 140 to 380,120 to 380, and 100-400. Higher viscosity fluid usually have higher VI.Viscosity index is determined according to ASTM Method D 2270-93 [1998]and the VI is related to kinematic viscosities measured at 40° C. and100° C. using ASTM Method D 445 method. All kinematic viscosity valuesreported for fluids herein are measured at 100° C. unless otherwisenoted. Dynamic viscosity can then be obtained by multiplying themeasured kinematic viscosity by the density of the liquid. The units forkinematic viscosity are m²/s, commonly converted to cSt. or centistokes(1 cSt.=10⁻⁶ m²/s or 1 cSt=1 mm²/sec). Lube VI and pour point aredependent on lube viscosity. For the most valid comparison of VI andpour point, it is best to compare fluids with similar viscosities at thesame temperature.

One embodiment according to the present invention is a new class ofpolyalpha-olefins having a unique chemical composition which ischaracterized by a high percentage of unique tail-to-tail connections atthe end position of the polymer. The new poly-alpha-olefins afterhydrogenation, when used by themselves or blended with another fluid,have unique lubrication properties. Or these new poly-alpha-olefinswithout hydrogenation can be further functionalized at the unsaturationposition with other reagents, such as aromatics, maleic anhydride, etc.The term “tail-to-tail connection” refers to a connection formed in thePAO oligomer in which the linear alpha-olefins incorporated into anoligomer are connected to one another via the alpha carbon, i.e., themethylene vinyl carbon of a linear alpha-olefin. The polyalpha-olefinssynthesized from the polymerization reaction contain unsaturation, whichcan be conveniently measured by bromine number (ASTM D 1159 orequivalent method) or NMR methods. Typically the bromine number willchange as a function of the polymer molecular size or viscosity. Thebromine number for the polymer will range from 70 to 0. When the brominenumber is below 1 or 2, the product can be used as is, without furtherhydrogenation. In many cases, when there is a need to reduce to brominenumber to below 2, or to below 0.3, or to tailor the tacticity of thepolymer, the polymers are then further hydrogenated with a hydrogenationcatalyst and a high pressure of hydrogen gas to reduce the unsaturationto give product with a bromine number less than 0.3

Another embodiment according to the present invention is a new class ofhydrogenated polyalpha-olefins having a unique chemical compositionwhich is characterized by a high percentage of unique tail-to-tailconnection at the end position of the polymer and by a reduced degree ofisotacticity compared to the product before hydrogenation.

The PAOs produced according to this invention are typically dimer,trimer, tetramer or higher oligomers of any two monomers from C₃ to C₃₀linear alpha-olefins. Alternatively, an alpha-olefin with alkylsubstituent at least 2 carbons away from the olefinic double bond, suchas 4-methyl-1-pentene, can also be used or alpha-olefins containingaromatic substituents two carbons away from the olefins. Examples are4-phenyl-1-butene or 6-phenyl-1-hexene, etc. Typically the PAOs producedherein are usually a mixture of many different oligomers. The smallestoligomers from these alpha-olefins have carbon numbers ranging from C₆to C₂₀. These small oligomers are usually too light for most highperformance fluids application. They are usually separated from thehigher oligomers with carbon number of greater than C₂₀ (for example C₂₄and higher are more preferred as high performance fluids). Theseseparated C₁₀ to C₂₀ oligomer olefins or the corresponding paraffinsafter hydrogenation can be used in specialty applications, such asdrilling fluids, solvents, paint thinner, etc., with excellentbiodegradability, toxicity, viscosities, etc. The fraction of C₂₀ toC₆₀, or preferably C₂₄ to C₅₀, or more preferably C₂₈ to C₄₅, or mostpreferably C₃₀ to C₄₀ can be used as high performance fluids. Typically,they have superior performance attributes, making them beneficial forspecific applications: such as lower viscosity for better fuel economy,better biodegradability, better low temperature flow properties, orlower volatility.

The higher viscosity products usually have much higher average degree ofpolymerization, and have very low amounts of C₂₄ and lower components.These high viscosity fluids are excellent blend stocks for lubeapplication to improve the viscosity. Because of their usually narrowmolecular weight distribution, they have superior shear stability.Because of their unique chemical composition, they have excellentviscometrics and unexpected low traction properties. These higherviscosity PAOs can be used as superior blend stocks. They can be blendstocks with any of the Group I, II, III, III+, GTL and Group V fluids,to give optimum viscometrics, solvency, high- and low-temperaturelubricity, etc. When further blended with proper additives, includingantioxidants, antiwear additives, friction modifiers, dispersants,detergents, corrosion inhibitors, defoamants, extreme pressureadditives, seal swell additives, and optionally viscosity modifiers,etc., the finished formulated lubes can be used as automotive engineoils, gear oils, industrial oils, or grease. Description of typicaladditives and synthetic lubricants can be found in the book “LubricantAdditives” Chemistry and Applications, ed. L. R. Rudnick, Marcel Dekker,Inc., New York, 2003, and Synthetic Lubricants and High-PerformanceFunctional Fluids, 2^(nd) ed. By L R. Rudnick and R. L. Shubkin, MarcelDekker, Inc., New York, 1999.

EXPERIMENTAL

The following examples are meant to illustrate the present invention andprovide a comparison with other methods and the products producedtherefrom. Numerous modifications and variations are possible and it isto be understood that within the scope of the appended claims, theinvention may be practiced otherwise than as specifically describedherein.

The alpha-olefins used for all the experiments, either individually orpre-mixed, were purified by mixing 1 liter of un-treated raw materialwith 20 grams of activated 13× molecular sieve and 10 grams ofde-oxygenation catalyst (a reduced copper catalyst) for at least twodays inside a glove box. The molecular sieve and de-ox catalyst werethen removed by filtration. This treated individual alpha-olefins werethan combined to give the desirable composition. Similarly, thispurification can be carried out by pumping a stream of thealpha-olefins, either alone or pre-mixed, through a bed of activated 13×molecular sieve alone, or through a bed of activated 13× molecularsiever followed by a bed of de-oxygenated catalyst, prior to enteringreactor. Sometimes for convenience, this purification can be carried outby pumping a stream of the alpha-olefins, either alone or pre-mixed,through a bed of activated 13× molecular sieve followed by a bed ofactivated alumina, prior to entering the reactor.

To test the flowability of the fluid after it is subjected to lowtemperature, a test was developed wherein a 10-30 ml liquid sample ofpolymer was soaked in crushed dry ice for at least two hours, followedby a slow warming to room temperature. Some materials may remain solideven after warming to room temperature, whereas others will becomefree-flowing liquids after warm-up to room temperature. This test isreproducible and provides a convenient method for comparinglow-temperature behavior of the fluids.

Example 1

An olefin mixture containing 18.4% 1-hexene, 22.3% 1-octene, 21.6%1-decene, 16.8% 1-dodecene, 10.4% 1-tetradecene, 6.4% 1-hexadecene and4% 1-octadecene was used as feed. This composition is similar to thelinear alpha-olefins produced from a typical LAO plant. 30 grams of thisolefin mixture and 0.522 gram of a toluene solution containing 20 mg oftriisobutylaluminum (TIBA)/g of toluene were charged into a reactor. Acatalyst solution containing 11 grams toluene, 0.0133 grams TIBA stocksolution, 0.30798 mg rac-dimethylsilylbis(tetrahydroindenyl) zirconiumdichloride (A) and 0.5408 mg N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate (B) was added to the reactor withstirring while maintaining a temperature of 30° C. After 19 hoursreaction time, the reaction was terminated by addition of 3 mlisopropanol, followed by washing with 120 ml 5% sodium hydroxidesolution in water. The isolated organic layer was distilled at 160° C./1millitorr vacuum for two hours to remove light ends and to isolate thelube fraction. The total lube yield was 85%. The recovered lubeproperties are summarized in Table 1.

Example 2

Similar to Example 1, except a metallocene containing 70% meso- and 30%racemic-dimethylsilylbis(tetrahydroindenyl) zirconium dichloride (C) wasused in the preparation.

Example 3

Similar to Example 1, except the reaction was carried out at 60° C.

Example 4

Similar to Example 2, except the reaction was carried out at 60° C.

Example 5

An olefin mixture containing 33.6 grams 1-octene, 42.0 grams 1-deceneand 50.4 grams 1-dodecene was charged into a round bottom flask andheated to 70° C. under an N₂ atmosphere. A catalyst solution containing2.34 grams 10 wt % MAO in toluene solution, 60 grams toluene and 3.7 mgof Catalyst A was added slowly to the olefin mixture while maintainingconstant temperature. The reaction was continued for 4 hours. Gaschromatography showed that 94% of the starting olefins were converted.The reaction was quenched by addition of 3 ml isopropanol, followed bywashing with 120 ml 5% sodium hydroxide solution in water. The isolatedorganic layer was distilled at 160° C./1 millitorr vacuum for two hoursto remove any light ends. The lube properties are summarized in Table 1.

Example 6 is a Comparative Example

An identical reaction was carried out as Example 5, except a pure1-decene was used as feed. The lube properties are summarized inTable 1. This fluid in the lab flowability test remained a solid afterwarming up to room temperature.

Examples 1-5 demonstrated that one can produce lube base stocks of wideviscosity ranges with superior VI and pour points from wide range ofmixed alpha-olefins, ranging from C₈-C₁₂ to C₆-C₁₈. Compared withExample 6, the fluids made from mixed alpha-olefins as described inExample 1-5 had distinctly better flowability. These two examplesdemonstrated the advantages of using mixed alpha-olefins as feeds forthis metallocene chemistry.

Example 7

An olefin mixture containing 7.1% 1-hexene, 9.5% 1-octene, 11.9%1-decene, 14.3% 1-dodecene, 16.7% 1-tetradecene, 19.1% 1-hexadecene and21.4% 1-octadecene was used as feed. 30 grams of this feed was chargedinto a reactor at 31° C. A catalyst solution containing 0.195 grams of10 wt % MAO in toluene, 9.7 grams toluene, and 0.308 mg of catalyst A,was added to the reactor. After 3 days, the reaction was worked up in amanner similar to the previous example. The lube product properties arelisted in Table 1.

Example 8

Similar to Example 1, except the feed composition was as described inExample 7.

Example 9

Similar to Example 7, except Catalyst C was used

Example 10

Similar to Example 1, except the feed composition was as described inExample 7, and the catalyst was Catalyst C.

Example 11

Similar to Example 7, except the reaction temperature was 60° C.

Example 12

Similar to Example 8, except the catalyst was catalyst C and thereaction temperature was 60° C.

FIGS. 1 and 2 compare the VI and pour points of the lubes made frommixed olefins with those made from 1-decene. This graph shows that themixed-olefin lubes have VI and pour points similar to the1-decene-derived lubes. The examples in Table 1 further demonstrate thatthese mixed-olefin-derived lube products demonstrated flowable behaviorin the cooling/warming cycle test. These results are not expected fromprior art. These fluids can be used as lubricant base stocks or as blendstocks with other lube base stocks to improve the properties of thelatter.

In summary, the examples in this patent memo demonstrate that one canuse a broad spectrum of LAOs as feeds to produce high quality lubricantbase stocks using metallocene polymerization catalysts. This inventionsignificantly broadens the options for feed sources for generating highquality synthetic fluids. Furthermore, these examples demonstrate thatwe can use the whole mixture of LAO from an ethylene growth process(Scheme 1). This process scheme may significantly improve the syntheticbase stock process economics. These examples demonstrate that the lubeproducts made from mixed LAO feeds have unexpected, superior, flowproperties.

TABLE 1 Lube Property Summary Example 1 2 3 4 5 6 7 8 9 10 11 12 Kv@100°C. 579.61 142.17 170.37 79.66 105.97 122.45 335.67 312.26 130.66 93.15151.83 19.48 (cSt) Kv@40° C. 7266.0 1346.4 1777.9 672.6 961.7 1080.53435.8 2249.6 1087.6 723.8 1376.2 119.2 (cSt) VI 259 210 208 195 200 218249 289 221 213 218 175 Pour Point, −27 −42 −39 −40 −39 −31 −6 −3 −3 −30 −3 ° C. Flow test flow flow flow flow flow No flow flow flow flow flowflow flow

Example 13

Similar to Example 7, except 0.308 mg of a catalystmeso-ethylenebis(1-indenyl)zirconium dichloride (Catalyst D) was usedand reaction was carried out at 30° C. The lube product properties weresummarized in Table 2.

Example 14

Similar to Example 13, except the reaction was carried out at 60° C.

Example 15

Similar to Example 13, except 0.308 mg of a catalystrac-ethylenebis(1-indenyl)zirconium dichloride (Catalyst E) was used.

Example 16

Similar to Example 15, except the reaction was carried out at 60° C.

Examples 13 to 16 demonstrated that other metallocene catalysts are justas effective for polymerization of mixed alpha-olefins to give high VIfluids.

TABLE 2 Example Example Example Example 13 14 15 16 Kv at 100° C., cSt804.16 917.13 727.84 648.15 Kv at 100° C., cSt 8292.3 9870.2 7878.97336.7 VI 302 306 290 278

Examples 17 to 21

Similar to Example 1 or Example 5, except a mixture of 1-hexene and1-tetradecene was used as feed. By adjusting the reaction temperature,we obtained 12-15 cSt fluids. Their properties and process data aresummarized in Table 3. Examples 17 to 20 are polymers from mixed linearalpha-olefins (C₆ and C₁₄), and have superior VI and pour points. Thereaction conversions were high and selectivity to lube products wereabove 75%. All these lube products have much higher VI than lube Example21 made from pure 1-hexene.

TABLE 3 Example 21 - com- parative 17 18 19 20 example Catalyst Type A +MAO A + MAO A + B A + B A + B Wt % C₆ 75.0 60.5 60.5 30.0 100.0 Wt % C₁₄25.0 39.5 39.5 70.0 0.0 Average C_(x) 7 7.75 7.75 10 6 Reaction Temp,140 140 100 100 120 ° C. Kv 100° C., cSt 14.62 14.96 14.04 13.52 12.02Kv 40° C., cSt 110.18 107.89 99.62 85.67 96.66 VI 126 134 133 150 105Pour Point, ° C. −48 −36 −36 −18 −43 Conversion, wt % 86.6 84.2 93.992.9 na Wt % Selectivity 76.6 81.6 82.0 91.4 na to lube

In Table 4, Examples 23 to 25 used 1-hexene and 1-dodecene as feed.Example 26 used 1-hexene and 1-hexadecene as feed. In all cases, theproduct lubes have excellent VI and pour points, exceeding the VIobtained with pure 1-hexene feed.

TABLE 4 Example 23 24 25 Example 26 Catalyst Type A + MAO A + B A + BCatalyst Type A + B Wt % C₆ 60.0 40.4 20.0 Wt % C₆ 77.1 Wt % C₁₂ 40.059.6 80.0 Wt % C₁₆ 22.9 Average C_(x) 7.5 8.55 10 Average C_(x) 7Reaction Tem, 140 100 100 Reaction Tem, 100 ° C. ° C. Kv 100° C., 15.7116.03 17.18 Kv 100° C., 19.13 cSt cSt Kv 40° C., 118.92 111 115.9 Kv 40°C., 161.22 cSt cSt VI 130 144 152 VI 126 Pour Point, −57 −54 −39 PourPoint, −30 ° C. ° C. Conversion, 87.4 84.5 91.2 Conversion, 83.2 wt % wt% Wt % Selec- 74 91.1 94.3 Wt % Selec- 86.6 tivity to lube tivity tolube

In Table 5, Examples 27 to 30 used 1-hexene, 1-dodecene and1-tetradecene as feeds. Again, the products have superior VI and pourpoint properties, much better than comparative example 21 made from pure1-hexene.

TABLE 5 Example 27 28 29 30 Catalyst A + B A + B A + B A + MAO Wt % C₆64.9 30.4 24 40 Wt % C₁₂ 16.2 60.8 48 20 Wt % C₁₄ 18.9 8.8 28 40 AverageC_(x) 7.4 9.3 10 8.13 Reaction Tem, ° C. 100 100 100 140 Kv 100° C., cSt17.48 15.46 13.21 11.44 Kv 40° C., cSt 135.94 106.05 87.17 69.58 VI 132146 150 147 Pour Point, ° C. −55 −42 −33 −24 Conversion, wt % 84.6 86.791.2 na Wt % selectivity 84.9 92.6 91.4 na to lube

Similar runs using mixed olefins as feed produced high viscosityproducts with excellent VI and pour points. Results are summarized inTable 6.

TABLE 6 Example no. 31 32 33 34 35 36 37 38 A + MAO A + B A + MAO A + BA + B A + B A + B A + B Wt % C₆ 60.0 60.0 60.5 30.0 41.7 60.5 100.0100.0 1-C_(n) olefin, n = 12 12 14 14 14 14 0 0 Wt % C_(n) 40.0 40.039.5 70.0 58.3 39.5 0.0 0.0 Average C_(x) 7.5 7.5 7.75 10 9 7.75 6 6 RxnTemp, ° C. 100 50 100 70 60 50 80 45 Kv 100° C., cSt 42.19 661.55 45.670.2 295.72 625.24 53.57 269.21 Kv 40° C., cSt 409.2 11288 454.3 667.53841.8 10424 661.4 4900.3 VI 147 235 148 174 215 234 132 176 Pour Point,° C. −43 −24 −39 −18 −30 −24 −40 −24 M_(n) 1892 na 2025 3045 5875 na1613 na MWD 1.68 na 1.715 1.832 2.089 na 1.67 na % Conversion 92.6 96.789.1 92.5 92.8 96 93.5 % Lube Selectivity 92.3 100 95 98.2 100 100 95

Example 39

To a 600 ml autoclave dried under nitrogen, was charged 16.7 grams of amixture containing 60% 1-butene and 40% 2-butene and a solutioncontaining 90 grams 1-dodecene, 0.262 gram triisobutyaluminum (TIBAL)and 1.72 mg catalyst A. The autoclave was heated to 60° C. A solutioncontaining 20 gram toluene and 2.305 mg catalyst B was added into theautoclave. The reaction was continued for 6 hours and then quenched byaddition of 1 ml isopropanol and 10 gram of activated alumina. The lubeproduct was isolated by filtering and distillation under high vacuum toremove any light ends boiling below 150° C. at 0.1 millitorr. The finalproduct weighed 88 grams and properties are summarized in Table 7.

Examples 40 to 42

Similar to Example 39, except different amounts of feeds were used.

Example 43

Similar to Example 39, except 1-tetradecene was used as feed.

Example 44

Similar to Example 39, except 76.2 grams 1-hexadecene and 40 grams of abutene mixture containing 60% 1-butene and 40% 2-butene were used asfeed.

Example 45

Similar to Example 39, except 73.2 grams 1-octadecene and 44.7 grams ofa butene mixture containing 60% 1-butene and 40% 2-butene were used asfeed.

Examples 46 and 47

Similar to Examples 42 and 43, except different amounts of pure1-dodecene or 1-tetradecene and pure 1-butene were used as feeds. Datafrom Examples 39 to 47 are summarized in Table 7. These data demonstrateseveral key points: 1. high quality fluids with high VI and superiorpoint points were prepared by mixed feed from two LAOs, wherein one ofthem is an abundant 1-butene. 2. The mixed-olefin feeds can comprise LAOin and other internal olefins, such as Examples 39 to 45 demonstrate,that a mixed butene stream can be used just as well as a pure 1-butene(Examples 46 and 47). 3. The ¹³C and ¹H NMR analysis of the productpolymers demonstrated that the polymers are random copolymers with arandom distribution index greater than 90%. 4. The product monomercompositions as calculated from ¹H and ¹³C-NMR spectral data, and fromthe calculated Bernoullian compositions agree with each other, and withthe feed olefin composition. Such polymers are said to possess a highdegree of randomness in the monomer distribution. This randomness in apolyalpha-olefin is novel and contributes to the superior lowtemperature viscosity viscometrics. Conventional Ziegler orZiegler-Natta or supported chromium oxide catalysts usually would nothave such high degree of randomness. 5. Proton NMR analysis of thesesamples showed that a significant amount (10 to 20%) of the olefins are1,2-disubstituted olefins. The formation of such olefins most likelystems from tail-to-tail termination of the growing polyalpha-olefins.This unusual termination creates a unique unsaturation which may bebeneficial for subsequent functionalization reactions or for providing aless branched lube component (after hydrogenation) with more desirablelube properties.

TABLE 7 Example no. 39 40 41 42 43 44 45 46 47 60%1-Butene/40%2-butenes + LAO Feed pure 1-C4 feed mole % C₄ in feed 25.050.0 75.0 34.6 46.7 55.7 62.2 50.0 80.0 1-C_(n) olefin, n = 12 12 12 1214 16 18 12 14 Rxn Temp, ° C. 60 60 60 60 60 60 60 60 60 % Conversion89.3 93.2 95.4 91.1 89.4 94.9 88.1 92.1 94.6 Product Properties Kv 100°C., cSt 133.8 187.4 175.6 113.3 118.2 101.1 99.1 143.3 212.0 Kv 40° C.,cSt 1664.9 2835.3 3297.1 1270.0 1429.0 1205.1 1177.9 1840.5 3733.3 VI176 174 151 178 173 166 165 176 166 Pour Point, ° C. −36 −27 −24 −39 −153 9 −33 −24 End Group Vinylidene Distribution, mole % C₄ 49 60 77 40 5062 67 49 71 C_(n) 51 40 23 60 50 38 33 51 29 Product Composition, mole %by ¹H NMR (CH₃ deconvolution) C₄ 47.3 61.0 74.0 40.4 51.1 65.6 65.7 54.171.8 C_(n) 52.7 39.0 26.0 59.6 48.9 34.4 34.3 45.9 28.2 by ¹³C NMR (CH3integration) C₄ 47.5 58.3 74.2 37.9 49.5 57.3 63.2 47.7 70.0 C_(n) 52.541.7 25.8 62.1 50.5 42.7 36.8 52.3 30.0 by ¹³C NMR (S_(αα) CH₂Bernoulian fit) C₄ 53.6 63.6 77.9 45.0 57.2 64.6 71.2 55.3 75.3 C_(n)46.4 36.4 22.1 55.0 42.8 35.4 28.8 44.7 24.7 Diff after Minimization0.01 0.012 0.005 0.023 0.02 0.006 0.008 0.024 0.013 Ratio of av.Calculated C₄ in 1.98 1.22 1.01 1.18 1.13 1.12 1.07 1.05 0.91 product toC₄ in feed Olefin Distribution (mole %), olefins per 1000 Carbons vinyl0 1 0.9 0.5 0.9 2.1 1.7 0.8 0.9 1,2-disub 14.7 16.2 9.3 16.8 14.4 12.317.4 16.5 12.6 trisub 15.6 15.2 15.3 14.2 16.2 18.6 19.8 17.2 19.8vinylidene 69.6 67.6 74.5 68.5 68.5 67.1 61.1 65.5 66.7

The smaller the Diff number (defined earlier in this text), the closerthe lube polymer to an ideal Bernoullian random copolymer. These numbersare usually much less than 0.1 for the present invention, indicative ofvery random polymers. Furthermore, the amount of butene andalpha-olefins in the product compositions as analyzed by either ¹³C NMR,or by ¹H NMR are very similar to the feed compositions, which again isindicative of a highly random polymer composition. This is confirmed bythe ratio of 1-butene mole % in polymer to the 1-butene mole % in thefeed ranging from 0.91 to 1.98.

Furthermore, using Field-Desorption Mass Spectroscopy, we analyzed thelube samples from Examples 17, 18, 19, 20, 33 and 34 and found that thealpha-olefin content in the polymers is very similar to the feedcomposition, as shown in Table 8. Similarly, we calculated the randomdistribution index for this series of copolymers and found that theyhave very high degree of randomness, with the RD index ranging from 75%to 91%. Furthermore, the calculated mole fractions of 1-hexene and1-tetradecene in polymer composition correlate closely with the molefractions of 1-hexene and 1-tetradecene in the feeds, as shown in FIG.3. This high degree of correlation is an excellent indication of highdegree of randomness of the polymers.

TABLE 8 Example No. 17 18 19 20 33 34 Average C_(x) 7 7.75 7.75 10 7.7510 Mole fraction of Feed 1-Hexene 0.875 0.778 0.778 0.5 0.778 0.51-Tetradecene 0.125 0.222 0.222 0.5 0.222 0.5 Calculated Mole fraction*1-Hexene 0.85 0.73 0.74 0.5 0.76 0.5 1-Tetradecene 0.15 0.27 0.26 0.50.24 0.5 Calculated Best Fit P-Matrix* P_(HH) 0.85 0.75 0.73 0.48 0.770.53 P_(TT) 0.13 0.32 0.22 0.48 0.28 0.53 Calculated Randomness factor*χ 1.02 0.93 1.05 1.04 0.95 0.94 *Calculation was discussed in thedetailed description of the invention

From the data in Table 8, it is clear that the polymers made in thisinvention have a degree of randomness, χ, very close to 1, ranging from0.93 to 1.05.

In Examples 48 to 51, polyalpha-olefins of 40 to 90 cSt were made from1-hexene and 1-dodecene. The reaction conditions and lube properties aresummarized in Table 9. The 1-hexene and 1-dodecene contents in thepolymer product were analyzed by ¹³C NMR, and the results are alsosummarized in Table 9. The mole fraction of 1-hexene in the productscorrelates very well with the mole fraction of 1-hexene in feedcomposition (FIG. 4). This high degree of correlation indicates that thepolymers are highly random copolymers. These random copolymers haveexcellent VI and pour points.

TABLE 9 Catalyst Type A + MAO A + B A + B A + B Example 48 49 50 51C_(n), n = 12 12 12 12 Average C_(x) 7.5 9 10 10.5 Wt % C₆ 60.0 33.320.0 14.3 mole % C₆ in feed 75 50 33.3 25 Kv 100° C., cSt 42.19 85.6877.73 91.17 Kv 40° C., cSt 409.2 851.1 701.3 845.1 VI 147 178 185 190Pour Point, ° C. −43 −42 −39 −27 by ¹³C NMR Mole % hexene in polymer66.7 49.6 32.6 26.3 mole % dodecene in polymer 33.3 50.4 67.4 73.7

Comparison with prior art examples. In these experiments, analpha-olefin mixture of same composition as Example 1 was polymerized at35, 50 and 70° C. in the same procedures as Example 1 to produce fluidwith properties summarized in Example 52 to 54 in Table 10.

Example No. 52 53 54 Reaction Temp, ° C. 70 50 35 Kv 100° C., cS 88.79515.59 688.59 Kv 40° C., cS 844.71 6123.36 8533.71 VI 185 258 271 PP, °C. −45 −30 −27

Example 52 to 54 fluids were made from feed compositions similar toExample 21 A to D of prior art U.S. Pat. No. 4,827,073. FIG. 5 comparesthe pour points of the Example 52-54 fluids vs. prior art example 21 Ato D. This graph shows that at the same viscosity, the fluids of thisinvention have much lower pour points. The prior art examples have atleast 10° C. higher pour points. This is a clear indication that fluidsmade from this invention have more uniform monomer distribution and areadvantageous than prior art samples.

Table 11 summarizes the wt % conversion of C6 to C18 alpha-olefins andthe relative conversion to 1-hexene by different metallocene catalystsystems. This wt % conversion was calculated from the amount ofunreacted alpha-olefins in crude mixture analyzed by gas chromographequipped with a 60 meter boiling point capillary column. As these datademonstrated that the conversions of 1-C6 to 1-C18 olefin in eachexample were very similar to each other over a very wide range ofconversions from 14% to 72% average conversion. The relative conversionsrates of C6 to C18 alpha-olefins to 1-hexene range from 0.65 to 1.21 forall these catalyst systems over a wide range of conversions. Thisindicated that all the alpha-olefins, irrespective of their size, havesimilar reactivity. These data support our previous conclusion that themonomers are incorporated into the polymer at equal rates and that themonomers are distributed randomly in the polymers.

TABLE 11 Example Example Example Example 7 Example 8 Example 9 10 13 15Reaction Time, 3.0 4.2 17.5 5.0 6.0 5.0 Hours Wt % Conversion of EachIndividual Olefins 1-C6 33.4 53.6 50.5 29.5 16.7 74.6 1-C8 29.1 44.947.1 30.9 15.5 72.6 1-C10 29.5 44.2 48.3 35.8 14.0 74.0 1-C12 27.6 41.947.6 35.2 13.6 71.6 1-C14 27.7 41.6 48.5 34.3 15.3 69.4 1-C16 27.6 43.850.7 32.8 12.1 72.1 1-C18 29.3 42.3 52.1 31.5 10.8 69.6 Average 29.244.6 49.3 32.9 14.0 72.0 Conversion Relative Conversion to 1-Hexene 1-C61.00 1.00 1.00 1.00 1.00 1.00 1-C8 0.87 0.84 0.93 1.05 0.93 0.97 1-C100.88 0.83 0.96 1.21 0.84 0.99 1-C12 0.83 0.78 0.94 1.19 0.82 0.96 1-C140.83 0.78 0.96 1.16 0.92 0.93 1-C16 0.83 0.82 1.00 1.11 0.73 0.97 1-C180.88 0.79 1.03 1.07 0.65 0.93 Average 0.87 0.83 0.97 1.11 0.84 0.96Conversion

Thus, numerous specific examples of the production of high performancePAO fluids from mixed feed olefins, including substantial amounts ofolefins other than pure 1-decene or traditional decene-substitutes suchas 1-octene and 1-dodecene, have been set forth above.

The advantages of using these mixed olefin feeds will be immediatelyapparent to one of ordinary skill in the art in possession of thepresent disclosure. Among other advantages, it significantly increasesthe availability and the range of feed stocks useful for the PAOproduction, so that PAO production is not exclusively dependent on1-decene supply. Second, the use of wide-range mixed olefins as feedswith metallocene catalyst system allows production of a broad productslate, from PAO to HVI-PAO fluids. Third, the use of mixed olefins asfeeds yields new fluids with superior properties as lubricant orfunctional fluids. In embodiments, the superior properties include oneor more of: high VI, wide viscosity range, low pour points and otherexcellent low-temperature properties, low traction, superior oxidativestability, lubricant film-forming properties and superior shearstability, and the like. Surprisingly, some of these properties cannoteven be achieved using fluids made from pure 1-decene. Furthermore, thefluids made from the mixed olefins are excellent base stocks for use asthe major components (for example, greater than 50%) in the formulationof automotive engine lubricants, transmission, and gear lubricants,industrial lubricants (including circulation lubricants, gearlubricants, hydraulic fluids, turbine oils, pump/compressor oils,refrigeration lubricants, metal-working fluids), aerospace lubricantsand greases, etc.

The fluids made in this invention are also superior blend stocks (from0.1 wt % to 95%, preferably 20 wt % to 80 wt %) with Group I to Group Vfluids, and/or with GTL basestocks to give full-synthetic,semi-synthetic or part-synthetic lubricants for use in all possiblelubricant applications, including automotive lubricants, industriallubricants, and greases, as mentioned above. Because of theirintrinsically superior properties, these inventive fluids can impart,sometimes synergistically, high performance properties to the finishedblend product. Examples are the high shear stability, high VI, highfilm-forming properties, low-temperature viscosity, low traction,superior oxidative properties of the finished lubricants. The PAOsdisclosed in this invention are used in formulating lubricantcompositions and greases, as described above. Whether in minor or inmajor amounts, they are further combined with an effective concentrationof additives selected from typical lubricant composition additives suchas antioxidants, antiwear agents, rust inhibitors, extreme pressureagents, anti-foamants, dispersants and VI improvers. Greases areformulated by combining the base stock with a thickener such as alithium soap or a polyurea compound and one or more grease additivesselected from antioxidants, antiwear agents, extreme pressure agent anddispersants. More examples for formulations for products can be found inLubricants and Lubrication, Ed. By T. Mang and W. Dresel, by Wiley-VCHGmbH, Weinheim 2001.

Trademarks used herein are indicated by a ™ symbol or ® symbol,indicating that the names may be protected by certain trademark rights,e.g., they may be registered trademarks in various jurisdictions.

All patents and patent applications, test procedures (such as ASTMmethods, UL methods, and the like), and other documents cited herein areincorporated in their entirety by reference to the extent suchdisclosure is not inconsistent with this invention and for alljurisdictions in which such incorporation is permitted.

When numerical lower limits and numerical upper limits are listedherein, ranges from any lower limit to any upper limit are contemplated.While the illustrative embodiments of the invention have been describedwith particularity, it will be understood that various othermodifications will be apparent to, and can be readily made, by thoseskilled in the art without departing from the spirit and scope of theinvention. Accordingly, it is not intended that the scope of the claimsappended hereto be limited to the examples and descriptions set forthherein but rather that the claims be construed as encompassing all thefeatures of patentable novelty which reside in the present invention,including all features which would be treated as equivalents thereof bythose skilled in the art to which the invention pertains.

The invention has been described above with reference to numerousembodiments and specific examples. Many variations will suggestthemselves to those skilled in this art in light of the above detaileddescription. All such obvious variations are within the full intendedscope of the appended claims.

1-40. (canceled)
 41. A random liquid polyalpha-olefin containing atleast two types of branches with average branch length ranging from 2.1to 12 and further characterized by at least one of the parametersselected from (a) randomness factor between 0.7 and 1.4 determined bymass spectrometry; (b) a minimized Diff factor of less than 0.3 for theS_(αα) methlene peak, determined by NMR; (c) M_(n)=200-50,000; (d)M_(w)=200-80,000; (e) MWD=1 to 5; (f) a pour point below 10° C.; (g) aKV at 100° C.=1.5 to 5,000; and (h) a VI greater than or equal to 100.42. The random liquid polyalpha-olefin of claim 41, characterized by atleast two of the parameters selected from (a) through (h).
 43. Therandom liquid polyalpha-olefin of claim 41, characterized by at leastthree of the parameters selected from (a) through (h).
 44. The randomliquid polyalpha-olefin of claim 41, characterized by at least four ofthe parameters selected from (a) through (h).
 45. The random liquidpolyalpha-olefin of claim 41, characterized by at least five of theparameters selected from (a) through (h).
 46. The random liquidpolyalpha-olefin of claim 41, characterized by at least six of theparameters selected from (a) through (h).
 47. The random liquidpolyalpha-olefin of claim 41, characterized by at least seven of theparameters selected from (a) through (h).
 48. The random liquidpolyalpha-olefin of claim 41, characterized by all of the parameters (a)through (h).
 49. The random liquid polyalpha-olefin of claim 41,characterized by an average branch length of from 3 to
 10. 50. Alubricant comprising 1 wt % to 95 wt % of at least one random liquidpolyalpha-olefin according to claim
 41. 51. The lubricant of claim 50,further comprising a second basestock selected from the group consistingof API Groups I, II, III, IV or V, or a Fischer-Tropsch hydrocarbonderived lubricant.
 52. The lubricant of claim 51, characterized by apour point of below −20° C.
 53. The use of a random liquidpolyalpha-olefin according to claim 41 in a fully formulated lubricant.54. The use of a lubricant according to claim 50 in a gear or anapparatus comprising roller bearings. 55-84. (canceled)
 85. The use of alubricant according to claim 41 in an engine lubricant in an automobile,ship or a gas turbine. 86-88. (canceled)